Laminated film

Abstract

A laminated film having a resin layer X containing an antistatic agent on at least one surface of a thermoplastic resin substrate film, satisfying all of the following conditions (1) to (3). (1) The average content ratio of nitrogen atoms to carbon atoms per 1 nm of the resin layer X, calculated by the ratio of nitrogen to carbon (N / C) and the thickness (nm) of the resin layer X, is 0.0030 [nm]. ‑1 The nitrogen to carbon ratio mentioned above was calculated using the high-resolution Rutherford backscattering method (HR-RBS method). (2) The surface resistivity of the resin layer X is 1.0 × 10⁻⁶. 10 Ω / □ or less. (3) The surface free energy of the above resin layer X is 20.0 mN / m or more and less than 30.0 mN / m. It provides excellent peelability and antistatic properties of the surface layer, and further avoids pollution caused by organosilicon and shedding of antistatic materials, which can help improve the performance of electronic components and batteries.

Description

Technical Field

[0001] The present invention relates to a laminated film having a resin layer on at least one side of a substrate film. Background Technology

[0002] Plastic films are widely used as substrate films in various applications such as magnetic recording materials and packaging materials due to their excellent mechanical, electrical, dimensional stability, transparency, and chemical resistance. These plastic films are generally used in the form of laminated films in which a functional resin layer is applied to the surface by coating and curing a coating.

[0003] In particular, when used as a process film in the manufacture of electronic components, the process involves coating a resin layer of a polyester film with a coating agent such as a ceramic slurry (hereinafter referred to as the surface layer), drying it, and then peeling the surface layer off the polyester film. In this surface layer peeling process, films with excellent release properties are generally used, considering processability, and these films typically contain silicone compounds and amino resins within the resin layer (Patent Document 1). However, when these silicone compounds are contained within the resin layer, the surface free energy of the resin layer decreases, and therefore the coating properties of the ceramic slurry or other coating agents sometimes become poor.

[0004] Furthermore, given the recent trend towards miniaturization and high performance of electronic devices, there is a demand for high-quality release films with fewer foreign objects and defects. Research has been conducted, for example, by adding antistatic materials to the release film to suppress the adhesion and stripping of foreign objects (Patent Document 2).

[0005] On the other hand, for release agents (hereinafter referred to as non-silicone release agents) with excellent coating properties, such as ceramic slurries, the technique of combining resins containing long-chain alkyl groups, olefin resins, fluorinated compounds, wax compounds, especially resins containing long-chain alkyl groups, with amino resins capable of forming dense cross-linked films and antistatic agents has been studied (Patent Document 3). Furthermore, release films exhibiting stable antistatic properties and excellent peeling properties have also been studied by using carbon-based antistatic agents such as carbon nanofibers (Patent Document 4). In addition, to address the problem of poor compatibility between polythiophene-based antistatic agents and silicone-based release agents, research has been conducted on providing an antistatic layer on a substrate film, followed by providing a release layer on the antistatic layer or on the other side (Patent Document 5). Furthermore, to obtain a release film with excellent peeling properties without peeling and charging, a release film with a release layer on one side of a polyester film and an antistatic layer on the other side has been studied (Patent Document 6). On the other hand, Patent Document 7 proposes an antistatic film in which a conductive layer containing carbon nanotubes (A), carbon nanotube dispersant (B), adhesive resin (C) and acrylic resin (D) having alkyl chains with 12 or more carbon atoms is provided on at least one side of a thermoplastic resin film. This film has antistatic properties and is also stain-resistant, allowing the adhered adhesive layer to be easily wiped off.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2017-105092

[0009] Patent Document 2: Japanese Patent Application Publication No. 2020-023690

[0010] Patent Document 3: Japanese Patent Application Publication No. 2019-131826

[0011] Patent Document 4: Japanese Patent Application Publication No. 2007-190717

[0012] Patent Document 5: International Publication No. 2016 / 133092

[0013] Patent Document 6: Japanese Patent Application Publication No. 2000-158611

[0014] Patent Document 7: Japanese Patent Application Publication No. 2010-072423 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] The inventors have studied the above-mentioned technology and found that when using the formulations of Patent Documents 1 and 2, which use silicone compounds as release agents, as process films in the manufacture of electronic components, problems sometimes arise in the process of coating a surface layer such as a ceramic slurry onto the resin layer of the polyester film, drying it, and then peeling the dried surface layer off the polyester film, such as causing pitting or pinholes due to the silicone compounds. Furthermore, it has been determined that even when no major problems occur in the coating process, sometimes when the surface layer is peeled off the polyester film, the silicone compounds migrate to the surface layer side, leaving residues on the surface after the ceramic slurry is fired, thus adversely affecting the performance of the electronic components.

[0017] For the formulation in Patent Document 3, which avoids contamination caused by silicone compounds by using a non-silicone mold release agent, the antistatic properties depend on humidity, etc., and a sufficient resistance value cannot be obtained. Furthermore, when an electronically conductive antistatic agent unaffected by humidity is used in combination with an amino resin, it was confirmed that the antistatic properties deteriorated, resulting in an insufficient resistance value.

[0018] While the formulation in Patent Document 4, which uses carbon nanofibers as an antistatic material, achieves good antistatic properties, the insufficient cross-linking of the resin layer results in high peel strength for surface layers such as ceramic slurries. Consequently, during the process of peeling the surface layer from the polyester film, the surface layer sometimes breaks, and further, the carbon nanofibers detach and transfer to the surface layer side, sometimes adversely affecting the performance of electronic components.

[0019] Patent Document 5, which involves applying an antistatic layer to a substrate film and then applying a release layer to the antistatic layer or another side, presents challenges in terms of productivity and cost due to the need for multiple coating / drying processes. Furthermore, the formulation in Patent Document 6, which applies a release layer to one side of a polyester film and an antistatic layer to the other, sometimes fails to achieve sufficient charge suppression during ceramic slurry peeling. The inventors further investigated the technology described in Patent Document 7 and found that, regarding the "anti-fouling property of easily wiping away the attached adhesive layer," the surface layer is sometimes difficult to peel off in the method of peeling the surface layer from the polyester film, which is the target of this application.

[0020] In addition, in recent years, although studies have been conducted on the use of release films in the vapor deposition process of lithium-ion battery manufacturing and the coating and transfer process of electrolytes and electrodes in all-solid-state battery manufacturing, the release film is required to have heat resistance, solvent resistance, and antistatic properties in harsh environments such as vacuum and absolute dry conditions.

[0021] Therefore, in this invention, the goal is to provide a laminated film that offers excellent surface layer peelability and antistatic properties, and further eliminates contamination caused by silicone and the shedding of antistatic materials, thereby contributing to improved performance of electronic components and batteries. Furthermore, the laminated film of this invention also excels in terms of productivity and cost because it is processed by combining a resin composition containing a release agent and an antistatic agent in a continuous coating / drying process.

[0022] Methods for solving problems

[0023] To address the aforementioned issues, the present invention comprises the following configuration. That is,

[0024] [1] A laminated film having a resin layer X containing an antistatic agent on at least one surface of a thermoplastic resin substrate film, which satisfies all of the following conditions (1) to (3).

[0025] (1) The average nitrogen to carbon content ratio per 1 nm of the resin layer X, calculated using the nitrogen to carbon ratio (N / C) and the thickness of the resin layer X (nm), is 0.0030 [nm]. -1 The nitrogen to carbon ratio mentioned above was calculated by measuring the high-resolution Rutherford backscattering method (HR-RBS method).

[0026] (2) The surface resistivity of the resin layer X is 1.0 × 10⁻⁶. 10 Below Ω / □.

[0027] (3) The surface free energy of the resin layer X is above 20.0 mN / m and less than 30.0 mN / m.

[0028] [2] A laminated film having a resin layer X containing an antistatic agent on at least one surface of a thermoplastic resin substrate film, wherein the resin layer X contains a long-chain alkyl resin, a melamine compound and an acrylic resin.

[0029] [3] According to the laminated film described in [1] or [2], the antistatic agent contained in the resin layer X is a conductive carbon material.

[0030] [4] According to the laminated film described in [3], the antistatic agent contained in the resin layer X is carbon nanotubes.

[0031] [5] When the surface of the above-mentioned resin layer X was analyzed by time-of-flight secondary ion mass spectrometry according to any one of [1] to [4], the ratio (P / K) of the peak intensity (P) of the fragment derived from polydimethylsiloxane to the peak intensity (K) of the fragment detected at the maximum intensity is less than 0.01.

[0032] [6] In any one of [1] to [5], the laminated film comprises a long-chain alkyl resin as a release agent in the resin layer X, and the exothermic peak temperature (Tc) during the cooling process of heating the long-chain alkyl resin from 25°C to 200°C at 20°C / min using a differential scanning calorimeter (DSC) and cooling it from 200°C to -50°C at 20°C / min is 30°C or higher and 90°C or lower.

[0033] [7] The laminated film according to [6] contains a long-chain alkyl resin and a melamine compound in the resin layer X, and contains at least one resin selected from acrylic resin, polyester resin, epoxy resin and urethane resin.

[0034] [8] According to the laminated film described in [1] to [7], regarding the X-ray absorption fine structure (XAFS) spectrum of carbon K absorption edge (XANES) in the X-ray absorption fine structure (XAFS) spectrum of the resin layer X measured by the partial electron yield method, when the angle between the incident X-ray and the surface of the resin layer X is set as θ, and the spectral intensity of 293.5 eV is set as I(θ), I(15°)-I(90°)≥0.10 is satisfied.

[0035] [9] In any one of [2], [5] to [8], the long-chain alkyl resin is a block copolymer.

[0036]

[10] The laminated film according to any one of [1] to [9], wherein the thermoplastic resin substrate film is a polyester film comprising at least one of biomass raw material and recycled raw material.

[0037]

[11] According to the laminated film described in [1] to

[10] , a resin layer Y is provided on the side opposite to the resin layer X, and the surface resistivity value is 1.0 × 10⁻⁶ in any of the sides. 10 Below Ω / □.

[0038]

[12] According to the laminated film described in

[11] , carbon nanotubes are included in the above-mentioned resin layer Y.

[0039]

[13] The laminated films according to [1] to

[12] are used in the manufacturing process of electronic components or battery components.

[0040] The effects of the invention

[0041] According to the present invention, by providing a release laminated film that combines the light peelability and antistatic properties of the resin layer disposed in the laminated film, thus enabling good processability in the process of peeling off the surface layer, and without contamination caused by organosilicon or the shedding of the antistatic agent, it is possible to help improve the performance of electronic components and batteries. Detailed Implementation

[0042] As a first embodiment of the laminated film of the present invention, the resin layer X containing the antistatic agent needs to satisfy all the requirements of (1) to (3) below.

[0043] Regarding the first method, the meaning of each characteristic and examples of control methods will be explained first.

[0044] (1) The average nitrogen to carbon content ratio per 1 nm of the resin layer X, calculated using the nitrogen to carbon ratio (N / C) and the thickness of the resin layer X (nm), is 0.0030 [nm]. -1 The nitrogen to carbon ratio mentioned above was calculated by measuring the high-resolution Rutherford backscattering method (HR-RBS method).

[0045] (2) The surface resistivity of the resin layer X is 1.0 × 10⁻⁶. 10 Below Ω / □.

[0046] (3) The surface free energy of the resin layer X is above 20.0 mN / m and less than 30.0 mN / m.

[0047] As a first requirement of the resin layer X included in the laminated film of the present invention, the average content ratio of nitrogen atoms to carbon atoms per 1 nm thickness of the resin layer X, calculated by the ratio of nitrogen atoms to carbon atoms (N / C) and the thickness of the resin layer X (nm), must be 0.0030 [nm]. -1 The nitrogen-to-carbon ratio mentioned above was calculated by measuring using the high-resolution Rutherford backscattering method (HR-RBS method).

[0048] This section explains the atomic weights calculated using the High Resolution Rutherford Backscattering (HR-RBS) method. For laminated films, numerous methods exist for quantifying the bonding state and hardness of the resin layer surface. Examples include vibrational spectroscopy using infrared spectroscopy and indentation hardness analysis using nanoindentation. However, these methods struggle to separate the resin layer from the polyester film portion, which is equivalent to the substrate, and fail to suppress the influence of the polyester film portion to accurately grasp the characteristics of the resin layer. The HR-RBS method, however, provides a more accurate understanding of the resin layer's characteristics. When the test sample is a laminated film with a resin layer on one side of the polyester film, the HR-RBS method obtains surface structural information by analyzing the energy of He ions scattered from the back side (i.e., from the substrate layer direction) along the substrate layer direction, incident from the surface of the resin layer of the test sample. Using this method, elemental, depth, and concentration information of the resin layer surface can be obtained. Because this method is surface-sensitive, it is effective and highly accurate in analyzing the characteristics of surface-formed layers such as resin layers.

[0049] Specifically, the information obtainable through the HR-RBS method is the ionic strength (i.e., the number) of ions scattered with specific energies. Energy corresponds to elemental information, and ionic strength corresponds to the abundance of each element. Since ionic strength varies depending on the measurement conditions, it is effectively converted into the relative quantity of the element of interest.

[0050] As numerical values ​​characterizing the surface properties of resin layers composed of non-silicone materials, the inventors conducted research and discovered that by controlling the average nitrogen to carbon atom content ratio per 1 nm thickness of the resin layer X (calculated using the nitrogen / carbon atom ratio (N / C) and the thickness of the resin layer X (nm)) within a preferred range, the detachment of antistatic agents in resin layers using non-silicone mold release agents can be suppressed. Since nitrogen atoms are abundant at the reaction sites of organic compounds, they can be considered an indicator that effectively characterizes the film properties. On the other hand, since the absolute number of each element also increases or decreases depending on the thickness of the resin layer, it is necessary to convert it to a value per unit thickness to more accurately represent the properties of the resin layer.

[0051] The average nitrogen to carbon atom content ratio per 1 nm of the resin layer X, calculated using the nitrogen to carbon atom ratio (N / C) and the thickness of the resin layer X (nm), is 0.0030 [nm]. -1 As a result, the cross-linking density of resin layer X is improved, inhibiting the penetration of adhesive components contained in the slurry into the interior of resin layer X when coating with ceramic slurry or other coating agents, thus enabling easy peeling when the surface layer is removed. Furthermore, since the antistatic agent is retained inside resin layer X, the shedding of the antistatic agent can be suppressed.

[0052] The average ratio of nitrogen atoms to carbon atoms per 1 nm thickness of the aforementioned resin layer X is less than 0.0030 [nm]. -1 In some cases, for example, insufficient release properties may occur when peeling off the surface layer, or the antistatic agent may detach from the resin layer X. From the above perspective, in the laminated film of the present invention, the average ratio of nitrogen atoms to carbon atoms per 1 nm thickness of the resin layer X is preferably 0.0050 [nm]. -1 The value is above 0.0080 nm, more preferably 0.0080 nm. -1 The above. On the other hand, there is no particular upper limit to the average ratio of nitrogen atoms to carbon atoms per 1 nm of thickness of the resin layer X described above. When the resin layer X is composed of organic compounds, it is approximately 0.1000 [nm]. -1 This becomes the de facto upper limit, and from the perspective of feasibility, 0.0200 [nm] is preferred. -1It should be noted that the details of the determination of the nitrogen to carbon ratio (N / C) using the HR-RBS method will be described later.

[0053] In the laminated film of the present invention, the nitrogen-to-carbon ratio (N / C) calculated by the HR-RBS method, and the average nitrogen-to-carbon content ratio per 1 nm thickness of the resin layer X, can be controlled not only by adjusting the amount of components constituting the resin layer X, but also by adjusting the crosslinking state of the resin layer X, adjusting the film density by drying in the case of forming the resin layer X by a wet coating method, and using an online coating method for coating the resin layer X during the polyester film manufacturing process. Preferred compositions of the resin layer X constituting the laminated film of the present invention and preferred methods for manufacturing the laminated film will be described later.

[0054] As a second requirement of the resin layer X included in the laminated film of the present invention, the surface resistivity needs to satisfy 1.0 × 10⁻⁶. 10 Below Ω / □. If the surface resistivity is 1.0 × 10⁻⁶ 10 With a resistivity of Ω / □ or less, the adhesion of foreign matter and the peeling off of the surface layer caused by film charging can be suppressed. The preferred surface resistivity value is 1.0 × 10⁻⁶. 9 Ω / □ or less, more preferably 1.0×10 8 Below Ω / □. There is no specific lower limit; for general antistatic agents, the lower limit is 1.0 × 10⁻⁶. 2 Ω / □ is the practical lower limit. In order to control the surface resistivity value to the above range, methods such as adding antistatic agents and release agents in the preferred ranges described later, or using carbon-based antistatic agents can be used.

[0055] As a third requirement of the resin layer X included in the laminated film of the present invention, the surface free energy needs to be 20.0 mN / m or more and less than 30.0 mN / m. By making the surface free energy within the above range, the process of coating a surface layer such as ceramic slurry onto the resin layer X of the laminated film can be carried out without coating depressions, and the process of peeling off the surface layer can be carried out with light peeling.

[0056] The surface free energy of the resin layer X in this invention is preferably 22.0 mN / m or more and less than 28.0 mN / m, more preferably 24.0 mN / m or more and less than 26.0 mN / m.

[0057] When the surface free energy of resin layer X is less than 20.0 mN / m, coating depressions sometimes occur during the surface coating process, resulting in a reduced yield. Sometimes, due to the need for a large amount of release agent, the release agent and antistatic agent are transferred from resin layer X, which adversely affects the performance of electronic components. On the other hand, when the surface free energy of resin layer X is 30.0 mN / m or higher, the surface layer may break during the peeling process due to heavy peeling.

[0058] In order to control the surface free energy of resin layer X to the above-mentioned preferred range, for example, the following methods can be used: setting the angle between the incident X-ray and the surface of resin layer X as θ, setting the spectral intensity of 293.5 eV as I(θ) and controlling it to I(15°) - I(90°) ≥ 0.10, or using the preferred material described later as the release agent.

[0059] On the other hand, as a second aspect of the laminated film of the present invention, a laminated film having a resin layer X containing an antistatic agent on at least one surface of a thermoplastic resin substrate film requires that the resin layer X contains a long-chain alkyl resin, a melamine compound and an acrylic resin.

[0060] By adopting this configuration, the requirements of the nitrogen-to-carbon ratio (N / C) calculated using the high-resolution Rutherford backscattering method (HR-RBS) and the average nitrogen-to-carbon ratio, surface resistivity, and surface free energy per 1 nm of resin layer X thickness calculated using the thickness of resin layer X (nm) can be fully met. Therefore, the advantages of this invention—light peelability of the resin layer, antistatic properties, processability during the surface layer peeling process, suppression of contamination caused by organosilicon, and antistatic agent shedding—can be simultaneously achieved. It should be noted that preferred materials used in the laminated film of this invention will be described later.

[0061] <Substrate film, polyester film>

[0062] The laminated film of the present invention has a resin layer X on at least one surface of the substrate film. Hereinafter, the substrate film in the laminated film of the present invention will be described in detail. There are no particular limitations on the type of substrate film, but polyester film is suitable from the viewpoint of heat resistance and cost (hereinafter, polyester film used as a substrate film is sometimes referred to as "substrate film" or "substrate"). A polyester film refers to a film in which polyester is the main component; the main component refers to the component contained in more than 50 parts by mass when the total amount of resin constituting the film is set to 100 parts by mass.

[0063] In this invention, the substrate film may contain particles. When particles are included, their content is preferably 3.0 parts by weight or less relative to the total substrate film. By setting the particle content within the above range, a laminated film with excellent transparency can be obtained.

[0064] The polyester used in the substrate film of the laminated film of the present invention will be described below. First, polyester is a general term for polymers whose main chain has ester bonds. Preferably, a substance selected from at least one of polyethylene terephthalate, propylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, butylene terephthalate, propylene 2,6-naphthalenedicarboxylate, and α,β-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate is used as a constituent component.

[0065] The polyester film using the aforementioned polyester is preferably a biaxially oriented polyester film. A biaxially oriented polyester film refers to a polyester film oriented in two orthogonal directions, which displays a biaxially oriented pattern in wide-angle X-ray diffraction. Generally, biaxially oriented polyester films are obtained by stretching an unstretched polyester sheet or film approximately 2.5 to 5.0 times its length along both the longitudinal direction and the width direction orthogonal to the longitudinal direction, followed by heat treatment to achieve crystallization and orientation. Biaxially oriented polyester films exhibit excellent thermal stability, particularly dimensional stability, mechanical strength, and planarity.

[0066] In addition, various additives such as antioxidants, heat stabilizers, weather stabilizers, UV absorbers, organic slip agents, pigments, dyes, organic or inorganic microparticles, fillers, antistatic agents, nucleating agents, etc., can be added to polyester films to a degree that does not deteriorate their properties.

[0067] The thickness of the polyester film is not particularly limited and is appropriately selected according to the application and type. However, considering factors such as mechanical strength and operability, it is generally preferred to be 10–500 μm, more preferably 15–250 μm, and even more preferably 20–200 μm. Furthermore, the polyester film can be any of the following: a single-layer film, a composite film obtained by co-extrusion, or a film formed by laminating the resulting films using various methods.

[0068] The polyester film used in the substrate film of the laminated film of the present invention, which contains at least one of biomass raw materials and recycled raw materials, is preferred from the viewpoint of reducing environmental impact. Here, biomass refers to organic compounds derived from plants that have undergone photosynthesis with carbon dioxide and water. When biomass is burned, it is typically converted back into carbon dioxide and water; therefore, biomass can be utilized as a so-called carbon-neutral renewable energy source. Furthermore, biomass raw materials refer to polyesters containing structural units derived from biomass.

[0069] When biomass is defined as the proportion of plant-derived carbon atoms in the total carbon atoms, for example in a ethylene terephthalate unit, the biomass is theoretically 20% when only the ethylene glycol component is derived from plants. To achieve a biomass greater than 20%, the terephthalic acid also needs to be plant-derived, which, while increasing the environmental impact, raises production costs. Regarding the ethylene glycol and terephthalic acid components, components derived from petroleum and those derived from plants can be used together.

[0070] From the viewpoint of maximizing the reduction of environmental impact, the lower limit of the biomass content of the polyester constituting the membrane is preferably 5%, more preferably 10%, and even more preferably 13%. With a biomass content of 5% or more, the effect of reducing environmental impact can be expected. On the other hand, the higher the upper limit of the biomass content, the more preferred, considering only the reduction of environmental impact; 100% is the upper limit. However, from the viewpoint of balancing production costs and reducing environmental impact, practically 20% or less is preferred.

[0071] It should be noted that, as a well-known method for determining the presence or absence of biomass raw materials, one can cite, for example, the method described on the homepage of the Japan Bioplastics Association (http: / / www.jbpaweb.net / bp / ) using carbon isotopes (…). 14 Method C).

[0072] Recycled raw materials refer to polyester that has been recycled and reused once or multiple times as a chemical product. Examples of recycled raw materials used in the laminated film of this invention include, for instance, uncoated portions removed from both ends in the width direction during the manufacturing process of the laminated film, recycled products of other polyester films, and polyester products that have been distributed in a form different from the film, such as PET bottles. When manufacturing the laminated film of this invention, the proportion of recycled raw materials in 100 parts by weight of the polyester raw material (recycling rate) is preferably 90 parts by weight or less. By limiting the use of recycled raw materials to 90 parts by weight or less, the amount of highly crystalline polyester that has been used once as a chemical product is suppressed, thereby reducing the decrease in thermal properties, transparency, and coloration of the resulting laminated film.

[0073] <Resin Layer X>

[0074] From the viewpoint of achieving both excellent peelability and antistatic properties, the laminated film of the present invention has a resin layer X on at least one surface of the substrate film.

[0075] From the viewpoint of preventing contamination caused by organosilicon, it is preferable that the ratio (P / K) of the peak intensity (P) of the polydimethylsiloxane-derived fragment to the peak intensity (K) of the fragment detected at maximum intensity in the resin layer X of the laminated film of the present invention is less than 0.01 in time-of-flight secondary ion mass spectrometry (GCIB-TOF-SIMS).

[0076] When the peak intensity ratio (P / K) of the time-of-flight secondary ion mass spectrometry (GCIB-TOF-SIMS) is within the above-mentioned preferred range, since the resin layer X has a low content of polydimethylsiloxane, when the laminated film of the present invention is used as a process film for manufacturing electronic components, the organosilicon compounds derived from polydimethylsiloxane are less likely to migrate (transfer) to the product side, thus avoiding problems such as component defects in electronic components. From the viewpoint of feasibility, a value of less than 0.001 (lower limit of determination) is further preferred.

[0077] There are no particular limitations on the method of making the P / K of the resin layer X of the laminated film of the present invention within the above range. For example, a method using a release agent that does not contain silicone can be cited.

[0078] The laminated film of the present invention preferably satisfies the following condition regarding the X-ray absorption near-edge structure (XANES) spectrum of the carbon K absorption edge in the X-ray absorption fine structure (XAFS) spectrum of the resin layer X measured by partial electron yield method: when the angle between the incident X-ray and the X-plane of the resin layer is θ, and the spectral intensity of 293.5 eV is I(θ), I(15°) - I(90°) ≥ 0.10. I(15°) - I(90°) less than 0.10 indicates that the spectral intensity does not change relative to the angle θ between the incident X-ray and the X-plane of the resin layer, i.e., the irradiation direction of the X-ray, indicating that the orientation of the long-chain alkyl groups is not anisotropic. On the other hand, the resin layer X satisfying I(15°) - I(90°) ≥ 0.10 means that the orientation direction of the long-chain alkyl groups in the resin layer X is skewed, specifically, orientation along the vertical direction is promoted, thereby reducing the penetration of surface layer components such as ceramic slurry into the resin layer X and enabling good peelability of the surface layer. From the above perspective, a preferred value is I(15°)-I(90°)≥0.30, and a further preferred value is I(15°)-I(90°)≥0.50. By making I(15°)-I(90°) within the above-preferred range, the peel strength of the surface layer can be good. It should be noted that, as a method to achieve I(15°)-I(90°)≥0.10, an example is to include a resin layer X containing a release agent (A), and to adjust its type and amount. On the other hand, there is no particular limitation on the upper limit of I(15°)-I(90°), but the upper limit achievable by practical materials and processes is approximately 10.00 or less, preferably 1.00 or less. Details of the release agent (A) will be described later.

[0079] <Resin Layer Y>

[0080] The laminated film of the present invention can have a resin layer Y disposed on the side opposite to the resin layer X. By making the resin layer Y a layer containing an antistatic agent, it is possible to further suppress the stripping charge when the surface layer such as ceramic slurry is peeled off from the resin layer X.

[0081] The surface resistivity of resin layer Y is preferably 1.0 × 10⁻⁶. 10 Below Ω / □. If the surface resistivity is 1.0 × 10⁻⁶ 10 With a resistivity of Ω / □ or less, the adhesion of foreign matter caused by film charging and the charging during the peeling of the surface layer from the resin layer X can be suppressed. The preferred surface resistivity value is 1.0 × 10⁻⁶. 8 Ω / □ or less, more preferably 1.0×10 7 Below Ω / □. There is no specific lower limit, but for general antistatic agents, the lower limit is 1.0 × 10⁻⁶. 2 Ω / □ is the practical lower limit. In order to control the surface resistivity value to the above range, methods such as setting the amount of antistatic agent added to the preferred range described later, or using a carbon-based antistatic agent can be used.

[0082] <Coating Composition>

[0083] Hereinafter, preferred coating compositions for forming the resin layer of the laminated film of the present invention will be described.

[0084] <Mold Release Agent (A)>

[0085] Examples of release agents that can be used in the first embodiment of the resin layer X of the laminated film of the present invention include resins containing long-chain alkyl groups, olefin resins, fluorinated compounds, and wax compounds. Among these, resins containing long-chain alkyl groups are preferred in terms of exhibiting good release properties. On the other hand, from the viewpoint of adjusting the nitrogen-to-carbon ratio (N / C) of the resin layer X of the laminated film of the present invention, calculated by the HR-RBS method, and the average content ratio of nitrogen atoms to carbon atoms per 1 nm thickness of the resin layer X to a preferred range, it is preferable to include reactive functional groups as side chains in addition to long-chain alkyl groups. That is, a copolymer resin having long-chain alkyl groups and reactive functional groups is particularly preferred as the release agent of the present invention. Examples of reactive functional groups include hydroxyl, carboxyl, amino, glycidyl, isocyanate, vinyl, acryloyl, and methacryloyl groups, but from the viewpoint of compatibility with water, which is a preferred solvent described later, hydroxyl groups are particularly preferred.

[0086] From the viewpoint that the resin layer X functions as a release layer, the laminated film of the present invention preferably contains a long-chain alkyl resin as a release agent in the resin layer X, and the exothermic peak temperature (Tc) during the cooling process of heating the long-chain alkyl resin from 25°C to 200°C at 20°C / min using a differential scanning calorimeter (DSC) and then cooling it from 200°C to -50°C at 20°C / min is 30°C or higher and 90°C or lower. This exothermic peak temperature (Tc) is more preferably 35°C or higher and 80°C or lower, and even more preferably 40°C or higher and 70°C or lower. By having an exothermic peak temperature Tc of 30°C or higher and 90°C or lower, the long-chain alkyl groups of the release agent are easily vertically oriented, the surface free energy of the resin layer X can be controlled within a preferred range, and the surface layer exhibits good coatability and light peelability.

[0087] In a second embodiment of the resin layer X of the laminated film of the present invention, the resin layer X contains a long-chain alkyl resin as a release agent (A).

[0088] Compounds containing long-chain alkyl groups can be commercially available. Specifically, the "Asiarejin" (registered trademark) series manufactured by Asio Industries, Ltd., the "Pierreil" (registered trademark) series manufactured by Lion Specialty Microcars Co., Ltd., and the Rezem series manufactured by Chukyo Oils, Ltd., which are aqueous dispersions of long-chain alkyl groups, are all suitable. The mold release agent preferably has an alkyl group with 12 or more carbon atoms, and more preferably has an alkyl group with 16 or more carbon atoms. By having the alkyl group have 12 or more carbon atoms, hydrophobicity is improved, allowing for sufficient mold release performance as a mold release agent. There is no particular upper limit to the number of carbon atoms in the alkyl group, but it is preferred if it is 25 or less, as this facilitates manufacturing.

[0089] It should be noted that the presence or absence of alkyl groups with 12 or more carbon atoms can also be evaluated using the intensity of the substance corresponding to the alkyl group within the signal obtained by, for example, TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) from a laminated membrane. Furthermore, by using a cutting method employing ion sputtering, continuous measurements along the depth direction (thickness direction) can be performed, allowing for the evaluation of the distribution of alkyl-containing compounds.

[0090] The aforementioned release agent (A) is more preferably a block copolymer containing alkyl units. By using a block copolymer containing alkyl units as the release agent, the alkyl groups are easily oriented, allowing the surface free energy of the resin layer X to be controlled within a preferred range, resulting in good coatability and easy peeling of the surface layer. As for the manufacturing method of the block copolymer, there are no particular limitations on any living radical polymerization method other than atom transfer radical polymerization (ATRP). Various polymerization methods can be employed, such as reversible addition-fragmentation chain transfer polymerization (RAFT), polymerization using organotellurium compounds (TERP), polymerization using organoantimony compounds (SBRP), polymerization using organobismuth compounds (BIRP), and iodine transfer polymerization, as well as nitroxide radical polymerization (NMP). Among these, RAFT and NMP are preferred from the viewpoint of controllability and ease of implementation.

[0091] <Adhesive Resin (B)>

[0092] In the first embodiment of the resin layer X in the laminated film of the present invention, the adhesive resin (B) forming the resin layer X has an average nitrogen to carbon atom content ratio of 0.0030 per 1 nm, which is a parameter corresponding to the crosslinking density of the resin layer X. -1 The above-mentioned resin can be made of any material. As such a resin, at least one selected from acrylic resins, epoxy resins, and urethane resins is suitable, but acrylic resins are more preferred from the viewpoint of adjusting the crosslinking density of the resin layer X and the ease of introducing reactive functional groups. Examples of reactive functional groups include hydroxyl, carboxyl, amino, glycidyl, isocyanate, vinyl, acryloyl, and methacryloyl groups, but from the viewpoint of adjusting the crosslinking density of the resin layer X, a hydroxyl or carboxyl group is preferred, and a copolymer acrylic resin having both hydroxyl and carboxyl groups is particularly preferred.

[0093] In a second embodiment of the resin layer X of the laminated film of the present invention, the resin layer X contains an acrylic resin as an adhesive resin (B).

[0094] There are no particular limitations on the acrylic resins that can be used as adhesive resins (B). As constituent monomers, examples include alkyl acrylates, alkyl methacrylates (as alkyl groups, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, cyclohexyl, phenyl, benzyl, phenylethyl, etc.), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and other monomers containing hydroxyl groups, acrylamide, methacrylamide, N-methacrylamide, N... Monomers containing amide groups, such as methyl methacrylamide, N-hydroxymethyl methacrylamide, N,N-dihydroxymethyl methacrylamide, N-methoxymethyl methacrylamide, and N-phenylacrylamide; monomers containing amino groups, such as N,N-diethylaminoethyl acrylate and N,N-diethylaminoethyl methacrylate; monomers containing epoxy groups, such as glycidyl acrylate and glycidyl methacrylate; and monomers containing carboxyl groups, such as acrylic acid, methacrylic acid, and their salts (lithium salts, sodium salts, potassium salts, etc.). These monomers can be polymerized individually or copolymerized with other types of monomers.

[0095] The glass transition point (Tg) of the acrylic resin used in the adhesive resin (B) of the laminated film of the present invention is not particularly limited, but is preferably 0 to 90°C, more preferably 10 to 80°C. By using an acrylic resin with a Tg of 0°C or higher, mold release properties are maintained even under high temperature and high humidity conditions. Conversely, by using an acrylic resin with a Tg of 90°C or lower, cracking during stretching can be reduced in the preferred manufacturing method described later. Furthermore, the weight-average molecular weight of the acrylic resin is preferably 100,000 or more, more preferably 300,000 or more, which is preferred in terms of both film-forming properties and mold release properties.

[0096] Preferred acrylic resins used in the laminated film of the present invention include copolymers of hydroxyalkyl acrylate, acrylamide, N-hydroxymethylacrylamide, glycidyl methacrylate, and acrylic acid, and are particularly preferred copolymers of 2-hydroxyethyl acrylate and acrylic acid.

[0097] In addition, as an epoxy resin that can be used as an adhesive resin (B), for example, sorbitol polyglycidyl ether crosslinking agents, polyglycerol polyglycidyl ether crosslinking agents, diglycerol polyglycidyl ether crosslinking agents, and polyethylene glycol diglycidyl ether crosslinking agents can be used. As for epoxy resins, commercially available products can be used, such as epoxy compounds "Denacol" (registered trademark) EX-611, EX-614, EX-614B, EX-512, EX-521, EX-421, EX-313, EX-810, EX-830, EX-850, etc. manufactured by Nagasekec Co., Ltd., diepoxy / polyepoxy compounds (SR-EG, SR-8EG, SR-GLG, etc.) manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy crosslinking agent "EPICLON" (registered trademark) EM-85-75W, or CR-5L manufactured by Dai Nippon Inki Kogyo Co., Ltd., etc. Among these, water-soluble substances are preferred.

[0098] Furthermore, the urethane resin used as the adhesive resin (B) in the laminated film of the present invention is preferably a resin obtained by reacting a polyhydroxy compound with a polyisocyanate compound through a known polymerization method of urethane resins such as emulsion polymerization or suspension polymerization.

[0099] Examples of polyhydroxy compounds include polyethylene glycol, polypropylene glycol, polyethylene glycol / propylene glycol, polybutanediol, 1,6-hexanediol, 1,4-butanediol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaprolactone, polyhexamethylene adipate, polyhexamethylene sebate, polytetramethylene adipate, polytetramethylene sebate, trimethylolpropane, trimethylolethane, pentaerythritol, polycarbonate glycol, and glycerol.

[0100] As polyisocyanate compounds, examples such as 1,6-hexanediisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, adducts of toluene diisocyanate and trimethylene propane, and adducts of 1,6-hexanediisocyanate and trimethylolethane can be used.

[0101] <Crosslinking agent (C)>

[0102] In the first embodiment of the resin layer X in the laminated film of the present invention, the presence of a crosslinking agent (C) in the resin layer X is particularly preferred from the viewpoint of adjusting the nitrogen-to-carbon atom ratio (N / C) calculated by the HR-RBS method and the average nitrogen-to-carbon atom content ratio per 1 nm thickness of the resin layer X to ensure sufficient crosslinking reaction of the resin layer X. Examples of crosslinking agents (C) include melamine compounds, carbodiimide compounds, isocyanate compounds, etc. Azoline compounds, etc. Among them, melamine compounds have a high number of reactive functional groups per unit molecular weight, which form dense cross-links through high-temperature heating. When using a laminated film as a release film, it can provide a light peel when peeling off surface layers such as ceramic slurry from the laminated film, and can inhibit the shedding of antistatic agents.

[0103] As a melamine compound that can be used as a crosslinking agent (C), examples include melamine, hydroxymethylated melamine derivatives obtained by condensing melamine with formaldehyde, compounds that have been partially or completely etherified by reacting a lower alcohol with hydroxymethylated melamine, and mixtures thereof. Furthermore, the melamine compound can be any of a monomer or a condensate formed from polymers of two or more monomers, or a mixture thereof. The lower alcohol used for etherification can be methanol, ethanol, isopropanol, n-butanol, and isobutanol. Substances having imino, hydroxymethyl, or alkoxymethyl groups such as methoxymethyl or butoxymethyl as functional groups in one molecule include imino-type methylated melamine resins, hydroxymethyl-type melamine resins, hydroxymethyl-type methylated melamine resins, and fully alkyl-type methylated melamine resins. Of these, hydroxymethylated melamine resins are most preferably used.

[0104] In a second embodiment of the resin layer X of the laminated film of the present invention, the resin layer X contains a melamine compound as a crosslinking agent (C).

[0105] However, when an electronically conductive antistatic agent, such as a thiophene-based material, is selected as the antistatic agent contained in resin layer X and / or resin layer Y of the laminated film of the present invention, sometimes the non-shared electrons possessed by the N element of the amino resin are supplied to the electronically conductive antistatic material, thereby annihilating holes as individual positive charges and increasing the surface resistivity. Therefore, when using a thiophene-based material as the antistatic agent, carbodiimide compounds, isocyanate compounds, etc., are preferably selected as the crosslinking agent (C). Azoline compounds. That is, one preferred embodiment of the present invention simultaneously includes, as a crosslinking agent (C), a compound selected from carbodiimide compounds, isocyanate compounds, The composition includes at least one of the azoline compounds and a polythiophene compound described later as an antistatic agent (D).

[0106] Carbodiimide compounds that can be used as crosslinking agents (C) are compounds in which one or more carbodiimide groups are present in the molecule, or in a tautomeric relationship, and which are cyanoamino groups as functional groups. Specific examples of such carbodiimide compounds include dicyclohexylmethane carbodiimide, dicyclohexylcarbodiimide, tetramethylphenyldimethylcarbodiimide, and urea-modified carbodiimide, and mixtures of one or more of them may also be used.

[0107] Furthermore, examples of isocyanate compounds that can be used as crosslinking agents (C) include, for example, toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophthalimide diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, toluene diisocyanate adduct with glycerol, toluene diisocyanate adduct with trimethylolpropane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, and isophthalene diisocyanate.

[0108] Furthermore, since isocyanate groups readily react with water, it is suitable to use blocked isocyanate compounds, such as those with isocyanate groups masked by a blocking agent, considering the shelf life of the coating agent. In this case, by applying heat during the drying process after coating the polyester film with the resin composition for forming the resin layer, the blocking agent dissociates, exposing the isocyanate groups, and as a result, the crosslinking reaction proceeds.

[0109] In addition, it can be used as a crosslinking agent (C). Azoline compounds are compounds that have the following properties in this compound: The substance containing an azoline group as a functional group is preferably composed of at least one of the following: A monomer containing an oxazoline group, and obtained by copolymerizing at least one other monomer. Composed of copolymers with zoline groups.

[0110] As containing Azoline monomers can be used, such as 2-vinyl-2- Azoline, 2-vinyl-4-methyl-2- Azoline, 2-vinyl-5-methyl-2- Azoline, 2-isopropenyl-2- Azazoline, 2-isopropenyl-4-methyl-2- azazoline and 2-isopropenyl-5-ethyl-2- Azoline, etc., or a mixture of one or more of them can also be used. Among them, 2-isopropenyl-2- Azoline is also readily available industrially and is therefore suitable.

[0111] exist Among zoline compounds, those containing The monomer containing the zolyl group uses at least one other monomer that is capable of reacting with the monomer containing the zolyl group. Monomers for copolymerization of azolinyl monomers may include, for example, acrylates or methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc.; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc.; unsaturated nitriles such as acrylonitrile, methacrylonitrile, etc.; unsaturated amides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, etc.; olefins such as ethylene, propylene, etc.; halogen-containing α,β-unsaturated monomers such as vinyl chloride, 1,1-dichloroethylene, vinyl fluoride, etc.; and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene, etc. They may also be used in mixtures of one or more.

[0112] <Antistatic Agent (D)>

[0113] For the laminated film of the present invention, it is necessary to contain an antistatic agent (D) as a component of resin layer X and / or resin layer Y. The type of antistatic agent (D) is not particularly limited, and conductive carbon-based materials such as carbon nanotubes (hereinafter, CNTs), polymers with conductive structures such as polythiophene, and acidic polymers in a free acid state can be used alone or in combination. In the present invention, from the viewpoint of combining antistatic properties and peelability, conductive carbon materials are more preferred, and CNTs are particularly preferred.

[0114] One particularly preferred embodiment of the resin layer X and / or resin layer Y of the laminated film of the present invention comprises a resin containing long-chain alkyl groups as the release agent (A), an acrylic resin as the adhesive resin (B), a melamine compound as the crosslinking agent (C), and CNTs as an antistatic agent (D). A further preferred embodiment comprises a resin containing long-chain alkyl groups as a block copolymer as the release agent (A), a copolymer acrylic resin having both hydroxyl and carboxyl groups as the adhesive resin (B), a melamine compound as the crosslinking agent (C), and CNTs as an antistatic agent (D). With such a combination, it is possible to achieve both peelability and antistatic properties while adjusting the nitrogen-to-carbon ratio (N / C) calculated by the HR-RBS method and the average nitrogen-to-carbon ratio per 1 nm thickness of the resin layer X.

[0115] In this invention, CNT refers to a seamless (seamless) tube made of graphene sheets with a honeycomb structure composed solely of carbon atoms, rolled into a cylindrical shape. Essentially, graphene sheets rolled into a single layer are called monolayer CNTs, those rolled into two layers are called two-layer CNTs, and those rolled into three or more layers are called multilayer CNTs. The CNTs used in this invention are preferably any one of the following: straight or curved monolayer CNTs, straight or curved two-layer CNTs, straight or curved multilayer CNTs, or combinations thereof.

[0116] It should be noted that the so-called honeycomb structure refers to a network structure mainly formed by six-membered rings. In the structure of CNT, there can be ring structures other than six-membered rings, such as five-membered rings and seven-membered rings, in the curved parts of the tube and the closed parts of the cross section.

[0117] Regarding the CNTs used in this invention, from the perspective of conductivity, straight or curved single-layer CNTs, and straight and / or curved two-layer CNTs are preferred. Single-layer CNTs and two-layer CNTs are excellent in terms of dispersibility in solvents, durability, and manufacturing cost. On the other hand, for multilayer CNTs with three or more layers, while dispersibility and manufacturing cost are excellent, sufficient conductivity is sometimes not achieved.

[0118] Furthermore, the CNTs used in this invention preferably have a diameter of 1 nm or more. Moreover, the diameter of the CNTs is preferably 50 nm or less, more preferably 10 nm or less. If the upper limit of the diameter is within the above-mentioned preferred range, the CNTs are less likely to form a multilayer structure of 3 or more layers, and the conductive paths are less likely to diverge between layers, resulting in high conductivity. Furthermore, a large number of CNTs are not required, and the CNTs do not detach from resin layer X and / or resin layer Y, thus preventing transfer to surface layers such as ceramic paste and not degrading component performance; sufficient antistatic properties can be achieved with a small quantity. On the other hand, CNTs with a lower limit of the above-mentioned preferred range are easy to manufacture and readily available.

[0119] The aspect ratio of the CNTs used in this invention is preferably 100 or more. Furthermore, the aspect ratio of the CNTs is preferably 5,000 or less. By making the aspect ratio of the CNTs within the above range, the antistatic properties of resin layer X and / or resin layer Y can be improved. If the aspect ratio of the CNTs is within the above range, during the formation of resin layer X and / or resin layer Y, when using the online coating method described later, the CNTs are moderately unwound during the stretching process, the conductive paths between the CNTs are not interrupted, and a network with sufficient spacing can be formed between the CNTs. If such a network structure is formed, good antistatic performance can be achieved.

[0120] It should be noted that the aspect ratio is the value obtained by dividing the length (nm) of the CNT by the diameter (nm) of the CNT (length (nm) / diameter (nm) of the CNT).

[0121] CNTs possessing these properties are obtained through known manufacturing methods such as chemical vapor deposition, catalyst vapor deposition, arc discharge, and laser evaporation. During CNT production, fullerenes, graphite, and amorphous carbon are generated as byproducts. Furthermore, catalyst metals such as nickel, iron, cobalt, and yttrium remain; therefore, it is preferable to remove these impurities through purification. To remove impurities, ultrasonic dispersion treatment along with acid treatment such as nitric acid or sulfuric acid is effective. Furthermore, separation using a filter is further preferred for improving purity.

[0122] Single-layer and two-layer CNTs are generally finer than multilayer CNTs. If uniformly dispersed, they ensure a greater number of conductive paths per unit volume, resulting in high conductivity. On the other hand, sometimes a large number of semiconductor CNTs are formed as a byproduct depending on the manufacturing process. In such cases, it is necessary to selectively manufacture or sort conductive CNTs. Multilayer CNTs generally exhibit conductivity, but if the number of layers is too large, the number of conductive paths per unit weight decreases. Therefore, even when using multilayer CNTs, the CNT diameter is preferably 50 nm or less, more preferably 20 nm or less, and even more preferably 10 nm or less. Furthermore, when using single-layer or two-layer CNTs, a diameter of 20 nm or less, and even more preferably 10 nm or less, is preferred from the viewpoint of antistatic properties.

[0123] When using polythiophene compounds as antistatic agents (D), compounds with structures in which the 3 and 4 positions of the thiophene ring are substituted can be used, for example. Furthermore, compounds in which the oxygen atom is bonded to the carbon atoms at the 3 and 4 positions of the thiophene ring are also suitable. Substances in which the hydrogen atom or carbon atom is directly bonded to the carbon atom sometimes have difficulty in achieving aqueous coating. The aforementioned compounds can be manufactured, for example, by the methods disclosed in Japanese Patent Application Publication No. 2000-6324, European Patent No. 602713, and US Patent No. 5391472, but other methods are also possible.

[0124] For example, after obtaining 3,4-ethylenedioxythiophene using an alkali metal salt of 3,4-dihydroxythiophene-2,5-dicarboxylic acid ester as a starting material, potassium persulfate, ferric sulfate, and the previously obtained 3,4-ethylenedioxythiophene are introduced into an aqueous solution of polystyrene sulfonic acid to react with it, thereby obtaining a composition complexed with an acidic polymer such as polystyrene sulfonic acid and a polythiophene such as poly(3,4-ethylenedioxythiophene).

[0125] Furthermore, as an aqueous coating composition containing poly-3,4-ethylenedioxythiophene and polystyrene sulfonic acid, substances such as Baytron P sold by HCStarck (Germany) can be used.

[0126] On the other hand, examples of acidic polymers in their free acid state include, for example, high molecular weight carboxylic acids, high molecular weight sulfonic acids, and polyvinyl sulfonic acid. Examples of high molecular weight carboxylic acids include polyacrylic acid, polymethacrylic acid, and polymaleic acid. Furthermore, examples of high molecular weight sulfonic acids include polystyrene sulfonic acid, which is particularly preferred for its antistatic properties. It should be noted that the free acid can be in the form of a partially neutralized salt. Additionally, it can be used in the form of copolymerized with other monomers that can be copolymerized, such as acrylates, methacrylates, and styrene. The molecular weight of the high molecular weight carboxylic acid and high molecular weight sulfonic acid is not particularly limited, but from the perspective of the stability and antistatic properties of the coating agent, its weight-average molecular weight is preferably 1,000 or more and 1,000,000 or less, more preferably 5,000 or more and 150,000 or less. A portion may contain alkaline salts such as lithium salts and sodium salts, or ammonium salts, without impairing the characteristics of the invention. In the case of a salt with the polyanion neutralized, it can also be considered to function as a dopant. This is because polystyrene sulfonic acid, which acts as a very strong acid, reacts with ammonium salts through a neutralization equilibrium reaction, causing the equilibrium to shift towards the acidic side.

[0127] It should be noted that the preferred contents of the resin composition for forming the resin layer X of the laminated film of the present invention, the release agent (A), the adhesive resin (B), the crosslinking agent (C), and the antistatic agent (D) are as follows.

[0128] <Content ratio of each resin composition in resin layer X>

[0129] As the resin composition for forming resin layer X in this invention, the release agent (A) has a preferred content. Specifically, when the total amount of release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by mass, the release agent (A) is preferably 10 parts by mass or more and 50 parts by mass or less, more preferably 20 parts by mass or more and 40 parts by mass or less, and even more preferably 35 parts by mass or less. When the amount of release agent (A) is 10 parts by mass or more, the surface layer exhibits good peelability. On the other hand, when the amount of release agent (A) is 50 parts by mass or less, when used as a release film, the detachment of release agent (A) from the laminated film is reduced, and contamination caused by release agent (A) can be suppressed. Furthermore, when the amount of release agent (A) is 50 parts by mass or less, the reduction in the effect of antistatic agent (D) caused by excessive presence of release agent (A) on the surface can also be suppressed.

[0130] Furthermore, there is a preferred range for the content of the crosslinking agent (C). Specifically, when the total amount of the release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by mass, the crosslinking agent (C) is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 60 parts by mass or more. By satisfying the above-mentioned content of the crosslinking agent (C), it is easy to control the ratio of nitrogen atoms to carbon atoms (N / C) calculated by the HR-RBS method and the average content ratio of nitrogen atoms to carbon atoms per 1 nm thickness of the resin layer X to be within a preferred range, thereby improving the release properties of various adhered materials. On the other hand, regarding the upper limit of the content, although it depends on the mixing amount of the release agent (A) and adhesive resin (B), it is 90 parts by mass, preferably 85 parts by mass, and more preferably 75 parts by mass.

[0131] On the other hand, the mixing ratio of adhesive resin (B) can be adjusted in such a way that the contents of the release agent (A) and crosslinking agent (C) are preferred. However, when the total amount of release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by mass, if the amount of adhesive resin (B) is less than 5 parts by mass, it is sometimes difficult to support the resin layer X, resulting in the detachment of the resin layer X and deterioration of quality.

[0132] When the total amount of release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by mass, the content of antistatic agent (D) in the resin layer X used in this invention is preferably 0.05 parts by mass or more and 20.0 parts by mass or less. More preferably, it is 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably, it is 1.0 parts by mass or more and 10.0 parts by mass or less. If it is within the above preferred range, the resin layer X has sufficient antistatic properties. On the other hand, the cohesive force caused by the intermolecular forces of the antistatic agent (D) is not too high, and the dispersibility of the antistatic agent (D) is not reduced. Therefore, the uniformity of the resin layer X is maintained, the surface layer is not prone to heavy peeling, and the performance deterioration caused by the peeling of the antistatic agent (D) when it is made into electronic components can be effectively prevented.

[0133] <Content ratio of each resin composition in resin layer Y>

[0134] The laminated film of the present invention may have a resin layer Y disposed on the side opposite to the resin layer X. Preferably, the resin layer Y contains an adhesive resin (B), a crosslinking agent (C), an antistatic agent (D), and may contain a release agent (A).

[0135] When the total amount of release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by mass, the content of adhesive resin (B) in resin layer Y is preferably 5 parts by mass or more and 100 parts by mass or less. More preferably, it is 10 parts by mass or more and 90 parts by mass or less, and even more preferably, it is 20 parts by mass or more and 80 parts by mass or less. If the content of adhesive resin (B) in resin layer Y is within the above-mentioned preferred range, the failure to obtain antistatic properties due to poor film formation can be effectively prevented.

[0136] Regarding the content of the crosslinking agent (C) in the resin layer Y, when the total amount of the release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by mass, the crosslinking agent (C) is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 50 parts by mass or more. By satisfying the above-mentioned content of the crosslinking agent (C), the shedding of the antistatic agent (D) can be suppressed.

[0137] When the total amount of release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by weight, the content of antistatic agent (D) in resin layer Y is preferably 0.05 parts by weight or more and 900 parts by weight or less. More preferably, it is 0.5 parts by weight or more and 700 parts by weight or less, and even more preferably, it is 1.0 parts by weight or more and 500 parts by weight or less. By setting the content of antistatic agent (D) within the above range, antistatic properties can be imparted to resin layer Y.

[0138] Furthermore, when the resin layer Y contains a release agent (A), and the total amount of the release agent (A), adhesive resin (B), and crosslinking agent (C) is set to 100 parts by mass, the content of the release agent (A) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less. By keeping the release agent (A) within the above range, release properties can be imparted to the resin layer Y without compromising its antistatic properties.

[0139] In addition to the release agent (A), adhesive resin (B), crosslinking agent (C), and antistatic agent (D), the resin composition for forming resin layer X and / or resin layer Y of the laminated film of the present invention may also contain particulate components. Particularly when the resin layer X and / or resin layer Y of the laminated film of the present invention contains the release agent (A), the film surface is smooth, unlike conventional films, and the slip properties are increased. In the laminated film of the present invention, when the slip properties are so high that the winding performance deteriorates, by including such particulate components in the resin composition for forming resin layer X and / or resin layer Y, protrusions can be formed on the surface of resin layer X and / or resin layer Y, thereby improving the transportability.

[0140] As suitable particle components for use in the multilayer film of the present invention, examples include oxide particles of elements located on the diagonal line connecting boron (B), silicon (Si), arsenic (As), tellurium (Te), and astatine (At). Examples of such particle components include, for instance, SiO2, TiO2, ZrO2, ZnO, CeO2, SnO2, Sb2O5, indium-doped tin oxide (ITO), phosphorus-doped tin oxide (PTO), Y2O3, La2O3, and Al2O3. It should be noted that these particle components can be used individually or in combination of two or more. From the viewpoint of dispersion stability and refractive index, SiO2, TiO2, and ZrO2 are particularly preferred.

[0141] The particle composition used in the resin layer X and / or resin layer Y of the laminated film of the present invention preferably has a number-average particle size of 3 nm or more and 500 nm or less. More preferably, it has a number-average particle size of 20 nm or more and 400 nm or less, and even more preferably, it has a number-average particle size of 40 nm or more and 300 nm or less. Here, the number-average particle size refers to the particle size determined by transmission electron microscopy (TEM). Specifically, the number-average particle size is determined by measuring the outer diameter of 10 particles present in the image at a magnification of 500,000x, and repeating this process for a total of 100 fields of view to measure the outer diameter of a total of 100 particles. Here, the outer diameter refers to the maximum diameter of the particle (i.e., the longest diameter of the particle), and the same applies to particles with internal cavities. If the number-average particle size of the particle composition is 3 nm or more, there is a tendency for the van der Waals forces between particles to be suppressed and particle aggregation to be reduced. On the other hand, by having a number-average particle size of 500 nm or less, particle shedding from the resin layer X and / or resin layer Y can be reduced.

[0142] The manufacturing method of the particle component is not particularly limited. Examples include surface treatment of the particle component with an acrylic resin. Specifically, methods (i) to (iv) below can be exemplified. It should be noted that, in this invention, surface treatment refers to the treatment that causes the acrylic resin to be adsorbed / attached to all or part of the surface of the particle component. The desired effect can be obtained through any of the methods (i) to (iv) below.

[0143] (i) A method of adding a mixture of pre-mixed particulate components and acrylic resins to a solvent and then dispersing it.

[0144] (ii) A method for dispersing particulate components and acrylic resins sequentially in a solvent.

[0145] (iii) A method of pre-dispersing the particle components with an acrylic resin in a solvent and then mixing the resulting dispersion.

[0146] (iv) A method of adding an acrylic resin to the resulting dispersion after dispersing the particle components in a solvent.

[0147] Furthermore, as a dispersing apparatus, a dissolver, high-speed mixer, homogenizer, mill, ball mill, roller mill, sand mill, paint shaker, SC mill, ring mill, needle mill, etc., can be used. Suitable conditions for using the above apparatus are a rotational speed of the rotating shaft of 5 to 15 m / s and a rotation time of 5 to 10 hours. Furthermore, from the perspective of improving dispersibility, it is more preferable to use dispersing beads such as glass beads during dispersion. The bead diameter is preferably 0.05 to 0.5 mm, more preferably 0.08 to 0.5 mm, and even more preferably 0.08 to 0.2 mm. It should be noted that mixing and stirring can be carried out by hand-vibrating the container, or by using an electromagnetic stirrer, stirring blades, or by ultrasonic irradiation, vibration dispersion, etc.

[0148] The content of the particulate component in resin layer X and / or resin layer Y is preferably 0.5 parts by mass or more and 10 parts by mass or less relative to the total of 100 parts by mass of the release agent (A), adhesive resin (B), and crosslinking agent (C). More preferably, it is 1 part by mass or more and 7 parts by mass or less, and even more preferably, it is 2 parts by mass or more and 5 parts by mass or less. By making the content of the particulate component 0.5 parts by mass or more and 10 parts by mass or less relative to the total of the release agent (A), adhesive resin (B), and crosslinking agent (C), a suitable surface shape can be imparted without impairing the film-forming properties of resin layer X and / or resin layer Y. As a result, the desired transportability can be fully expressed.

[0149] Furthermore, a crosslinking catalyst may be included in the resin layer X and / or resin layer Y of the laminated film of the present invention. By including a crosslinking catalyst, the crosslinking reaction between the aforementioned binder resin (B) and the crosslinking agent (C) during heat treatment proceeds efficiently. The average content ratio of nitrogen atoms to carbon atoms per 1 nm, calculated by the nitrogen-to-carbon ratio (N / C) determined using the HR-RBS method and the thickness (nm) of resin layer X and / or resin layer Y, increases, i.e., the degree of crosslinking of resin layer X and / or resin layer Y becomes higher. As a result, when a surface layer is coated on resin layer X and / or resin layer Y, penetration of the surface layer into resin layer X and / or resin layer Y is less likely to occur, and good peelability of the surface layer is easily achieved. As a crosslinking catalyst, acidic catalysts such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, amine salt-based catalysts, etc., can be used.

[0150] In the case of preparing a resin composition, a solvent or dispersion medium (hereinafter referred to as "solvent") may be included. That is, various components can be dissolved or dispersed in a solvent to prepare a resin composition, which is then coated onto a polyester substrate. When such a method is used, a film with laminated resin layers can be obtained by drying the solvent after coating and then heating it.

[0151] For the laminated membrane of the present invention, an aqueous solvent is preferably used as the solvent. Here, an aqueous solvent refers to water, or a mixture of water and water with water-soluble organic solvents such as alcohols (methanol, ethanol, isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), ethylene glycol, diethylene glycol, propylene glycol, etc., in any ratio. This is because by using an aqueous solvent, rapid evaporation of the solvent during the heating process can be suppressed, resulting in the formation of a uniform resin layer X and / or resin layer Y, and also exhibiting excellent environmental performance.

[0152] In the laminated film of the present invention, the resin composition for forming the resin layer can be prepared by mixing and stirring a release agent (A), adhesive resin (B), crosslinking agent (C), antistatic agent (D), and aqueous solvent that have been dispersed or dissolved in water as needed, in any order and at a desired weight ratio. Subsequently, various additives such as slip agents, inorganic particles, organic particles, surfactants, antioxidants, and thermal initiators can be mixed and stirred in any order to a degree that does not deteriorate the properties of the resin layer X and / or resin layer Y formed by the resin composition. The mixing and stirring methods can include methods such as manually vibrating the container, stirring with an electromagnetic stirrer or stirring blades, using ultrasonic irradiation, or vibration dispersion.

[0153] <Manufacturing Method>

[0154] In the laminated film of the present invention, the method of providing resin layer X and / or resin layer Y on at least one side of the substrate film can be any of online coating method and offline coating method, preferably online coating method. Online coating method refers to a method of coating within the manufacturing process of the polyester film. Specifically, it refers to a method of coating at any stage from melt extrusion of polyester resin to biaxial stretching followed by heat treatment and rolling. Typically, coating is applied to any of the following films: an unstretched (unoriented) polyester film (A film) obtained after melt extrusion / quenching and is substantially amorphous; a uniaxially stretched (uniaxially oriented) polyester film (B film) subsequently stretched along the length direction; or a biaxially stretched (biaxially oriented) polyester film (C film) stretched further along the width direction before heat treatment.

[0155] On the other hand, the so-called offline coating method is a method of coating a resin composition onto a film (C film) after the above-mentioned A film is stretched along a uniaxial or biaxial direction and subjected to heat treatment to complete the crystal orientation of the polyester film. This process is different from the film-making process.

[0156] In this invention, the laminated film is preferably manufactured by an online coating method. By using an online coating method, for example, compared to forming resin layers X and / or Y on a biaxially stretched PET film by offline coating, not only can the laminated film be manufactured at a lower cost, but also dense crosslinking of resin layers X and / or Y can be promoted by implementing high-temperature heat treatment above 200°C, which is substantially impossible with offline coating. This inhibits the penetration of the binder components contained in the coating agent, such as ceramic slurry, into the interior of resin layers X and / or Y, thereby allowing for easy peeling when the surface layer is removed. Furthermore, the antistatic agent is retained within resin layers X and / or Y through dense crosslinking, thus inhibiting the shedding of the antistatic agent. In particular, a manufacturing method that completes the crystallization orientation of a polyester film by coating at least one side of the polyester film with a coating composition before the crystallization orientation is completed, stretching it at least in a uniaxial direction, and then performing heat treatment is preferred from the viewpoint of manufacturing cost and dimensional stability, heat shrinkage characteristics, and density of resin layer X and / or resin layer Y after heat treatment.

[0157] <Coating Method>

[0158] The resin composition can be coated onto the polyester film using any known coating method, such as bar coating, reverse coating, gravure coating, die coating, or scraper coating. Here, the adhesion between the polyester film and resin layer X and / or resin layer Y will be explained.

[0159] If resin layers X and / or Y are deposited on a polyester film using a conventional offline coating method, and if a release agent is included in resin layers X and / or Y, the low surface energy of these layers results in poor adhesion to the film. This can lead to resin layer shearing and deterioration of peel strength during film rewinding. However, when resin layers X and / or Y are laminated using an online coating method, a very small amount of the coating composition penetrates the polyester film before crystallization and orientation are complete. This imparts excellent adhesion between resin layers X and / or Y and the thermoplastic resin substrate. Consequently, superior peel strength is achieved.

[0160] <Methods for forming resin layer X and / or resin layer Y>

[0161] In this invention, resin layer X and / or resin layer Y are preferably formed by coating at least one side of a polyester film with the coating composition and then drying it. In this invention, when the coating composition contains a solvent, an aqueous solvent is preferred. By using an aqueous solvent, rapid evaporation of the solvent during the drying process can be suppressed, resulting in a uniform and high-quality resin layer X and / or resin layer Y, and also exhibiting excellent environmental impact.

[0162] Here, the term "aqueous solvent" refers to water, or water mixed with water-soluble organic solvents such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, propylene glycol, etc., in any ratio in which they are not separated.

[0163] The coating composition is applied to the film as described above, preferably by in-line coating. Specifically, this refers to a method of coating at any stage from the melt extrusion of polyester resin to heat treatment and rolling after biaxial stretching. Typically, coating is applied to any of the following films: an unstretched (unoriented) film (A film) obtained after melt extrusion / quenching and which is substantially amorphous; a uniaxially stretched (uniaxially oriented) film (B film) subsequently stretched along the length or width direction; or a biaxially stretched (biaxially oriented) film (C film) before heat treatment and further stretched along the width or length direction.

[0164] In this invention, it is preferable to use either the A film or the B film mentioned above, before the crystallization orientation is completed, to coat the coating composition. Then, the film is stretched in a uniaxial or biaxial direction and heat-treated at a temperature higher than the boiling point of the solvent to complete the crystallization orientation of the film while simultaneously forming the resin layer X and / or resin layer Y. According to this method, film formation and coating and drying of the coating composition (i.e., formation of resin layer X and / or resin layer Y) can be performed simultaneously. Therefore, in addition to the advantages in manufacturing cost, it is also easy to ensure the adhesion of the substrate.

[0165] The method of coating a film (B-film) that has been uniaxially stretched along its length direction with a coating composition, followed by stretching along its width direction and heat treatment, is superior. This is because, compared to a method that involves biaxial stretching after coating an unstretched film, the stretching process is reduced by one step. Therefore, defects and cracks in the resin layers X and / or Y caused by stretching are less likely to occur, resulting in resin layers X and / or Y with excellent smoothness. Furthermore, as described above, by coating the film with the coating composition before crystal orientation is completed, adhesion between the resin layers X and / or Y and the polyester film can be imparted.

[0166] Therefore, the preferred method for forming resin layer X and / or resin layer Y in this invention is to coat a coating composition using an aqueous solvent onto a polyester film using an online coating method, followed by drying and heat treatment. More preferably, a method is to online coat the coating composition onto a B film after uniaxial stretching. In the method for manufacturing the laminated film of this invention, drying can be performed in a temperature range of 80–130°C to ensure complete removal of the solvent from the coating composition. Furthermore, to ensure the formation of resin layer X and / or resin layer Y is completed by simultaneously completing the crystallization orientation of the polyester film and the thermal curing of the coating composition, heat treatment can be performed in a temperature range of 160–240°C. Particularly preferred is 180–240°C. When the heat treatment temperature is below 160°C, sometimes not only does the heat resistance of the substrate decrease, resulting in a reduction in the properties of the polyester as the substrate film, but it is also difficult to obtain dense crosslinking of resin layer X and / or resin layer Y, leading to deterioration of the surface layer's peelability and the shedding of the antistatic agent.

[0167] Furthermore, the concentration of solid components in the coating composition is preferably 40 parts by mass or less. By setting the concentration of solid components to 40 parts by mass or less, good coatability can be imparted to the coating composition, and a laminated film having a uniform resin layer X and / or resin layer Y can be manufactured.

[0168] It should be noted that the so-called solid component concentration refers to the proportion of the mass of the coating composition after deducting the mass of the solvent from the mass of the coating composition (i.e., [solid component concentration] = [(mass of coating composition) - (mass of solvent)] / [mass of coating composition]).

[0169] <Method for manufacturing laminated films>

[0170] Next, the manufacturing method of the laminated film of the present invention will be specifically described using the example of a polyethylene terephthalate (PET) film as the substrate film, but the laminated film of the present invention is not limited to the material obtained by this manufacturing method.

[0171] First, after thoroughly vacuum drying the PET granules, they are fed into an extruder and melt-extruded into sheets at approximately 280°C. The sheets are then cooled and solidified to produce an unstretched (unoriented) PET film (A film). This A film is then stretched 2.5 to 5.0 times its length using rollers heated to 80–120°C to obtain a uniaxially oriented PET film (B film). A coating composition prepared to a specified concentration is then applied to one side of the B film. Alternatively, the coated surface of the PET film can be subjected to surface treatments such as corona discharge treatment before coating. These surface treatments improve the wettability of the resin composition on the PET film, prevent depressions in the resin composition, and achieve a uniform coating thickness.

[0172] After coating, the ends of the PET film are held by clamps and guided to a heat treatment zone (preheating zone) at 80–130°C to dry the solvent in the coating composition. After drying, the film is stretched 1.1–5.0 times in the width direction. It is then guided to a heating zone (heat treatment zone) at 150–250°C for 1–30 seconds to complete crystallization orientation and simultaneously complete the formation of resin layer X and / or resin layer Y. It can be considered that the crosslinking of resin layer X and / or resin layer Y is promoted through this heating process (heat treatment process). It should be noted that during this heating process (heat treatment process), a relaxation treatment of 3–15% can also be performed in the width or length direction as needed. This operation yields a laminated film, which can also be wound into a roll to form a film roll.

[0173] Example

[0174] The laminated film of the present invention will be described in more detail below using examples, but the laminated film of the present invention is not limited thereto.

[0175] <Methods for determining characteristics and methods for evaluating effects>

[0176] The methods for measuring the properties and evaluating the effects of this invention are described below.

[0177] (1) The thicknesses dx and dy of resin layer X and resin layer Y

[0178] The laminated membrane was stained with RuO4 and / or OsO4. Next, the laminated membrane was frozen and cut parallel to its thickness direction to obtain 10 ultrathin section samples for observing the resin layer cross-section. Each sample cross-section was observed using a TEM (transmission electron microscope: Hitachi, Ltd. H7100FA type) at magnifications ranging from 10,000 to 1,000,000, obtaining cross-sectional photographs. The thickness of the resin layer was measured using the length measuring function of the microscope from these 10 cross-sectional photographs. The averaged values ​​were then set as the thickness dx of resin layer X and the thickness dy of resin layer Y of the laminated membrane.

[0179] (2) The ratio of nitrogen to carbon atoms (N / C) calculated by high-resolution Rutherford backscattering method (HR-RBS method), and the average content ratio of nitrogen to carbon atoms per 1 nm thickness of resin layer X.

[0180] Rutherford backscattering is an analytical method that obtains information about the elements in a sample by analyzing the energy of ions backscattered (Rutherford scattering) through collisions with elements in the sample after irradiating the sample with an ion beam. In addition to information about the types and numbers of elements that collided with the sample, the information obtained from analyzing the energy of the scattered ions includes relative information about their location (i.e., depth) based on the energy change up to the point of collision.

[0181] The measuring apparatus used was a Pelletron 3SDH manufactured by National Electrostatics Corporation. It delivered an energy of 2,300 keV and a beam diameter of... of 4 He ++ When ions are incident on the sample at an angle of 75° relative to the sample surface, the scattered ions will... 4 He ++ Ions were detected at scattering angles of 160° and 146° using a polarized magnetic field energy analyzer. The sample current was 7 nA, the irradiation dose was 40 μC, and the energy range was 200–1000 keV. The resulting spectra were simulated and fitted to a depth profile, and the surface density [atoms / cm³] was calculated. 2 It should be noted that, in order to reduce damage such as burns caused by the measurement, the measurements were performed at 10 staggered locations, and the accumulated data was used in the analysis. First, the obtained data was analyzed, and the data from the substrate and the data from the resin layer X were separated. Specifically, the nitrogen element (N) not contained in the substrate of the laminated polyester film of the embodiment of the present invention was used as an indicator, and the boundary between the substrate and the resin layer X was defined as the threshold at which the nitrogen element becomes undetectable. The analysis was performed based on the relative positional information. Next, the areal density of nitrogen element obtained from the resin layer [atoms / cm²] was analyzed. 2 Divide by the areal density of carbon (atoms / cm³) obtained similarly from the resin layer. 2 The ratio of nitrogen atoms to carbon atoms (N / C) was calculated. It was further divided by the thickness of resin layer X measured by (1) to set it as the average ratio of nitrogen atoms to carbon atoms per 1 nm of resin layer X.

[0182] (3) Surface resistivity value

[0183] Surface resistivity was measured after the laminated film was fabricated and placed at 23% relative humidity and 25°C for 24 hours. Under this atmosphere, a digital ultra-high resistance / micro-current meter R8340A and a 12702A (Advanced Technology Co., Ltd., main electrode: Φ50mm, counter electrode: Φ103mm) were used. A voltage of 100V was applied for 10 seconds before measurement. The unit of surface resistivity is Ω / □. The surfaces of resin layers X and Y of the laminated film, opposite to the substrate film, were evaluated, and the average of 10 measurements was taken as the surface resistivity value of the sample.

[0184] (4) Surface free energy

[0185] First, the laminated membrane was placed in an atmosphere of 23°C and 65% relative humidity for 24 hours. Then, under the same atmosphere, the contact angles of the resin layer X of the laminated membrane were measured at five points using a CA-D type contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) for four solutions: pure water, ethylene glycol, formamide, and diiodomethane. The average of the three measurements (excluding the maximum and minimum values) was taken as the contact angle for each solution.

[0186] Next, using the contact angles of the four solutions obtained, the analysis was conducted based on the principle proposed by Hata et al., which involves separating the surface free energy (γ) of a solid into a dispersion force component (γ). S d ), polar force component (γ) S p ), and hydrogen bonding components (γ) S h Using the geometric mean method of the extended Fowkes formula (extended Fowkes formula) for these three components, the dispersion force, polar force, hydrogen bond force, and surface energy as the sum of the dispersion force and polar force of the present invention are calculated.

[0187] The specific calculation method is shown below. The meaning of each symbol is described in the following text. In γ... S L When the tension at the interface between the solid and the liquid is , mathematical formula (i) holds.

[0188] γ S L : The surface energy of resin layer X and the known solutions listed in the table

[0189] γ S Surface energy of resin layer X

[0190] γ L The table lists the known surface energies of solutions.

[0191] γ Sd The dispersion force component of the surface energy of resin layer X

[0192] γ S p The polar force component of the surface energy of resin layer X

[0193] γ S h Hydrogen bonding force component of the surface energy of resin layer X

[0194] γ L d The table lists the dispersive force components of the known surface energies of solutions.

[0195] γ L p The table lists the polar force components of the known surface energy of solutions.

[0196] γ L h The table lists the hydrogen bonding force composition of known solutions with surface energies.

[0197] γ S L =γ S +γ L -2(γ S d ·γ L d ) 1 / 2 -2(γ S p ·γ L p ) 1 / 2 -2(γ S h ·γ L h ) 1 / 2 ...Mathematical expression (i).

[0198] Furthermore, the state when a smooth solid surface contacts a droplet at a contact angle (θ) is represented by the following formula (Young's formula).

[0199] γ S =γ S L +γ L cosθ··· mathematical expression (ii).

[0200] If we combine these mathematical expressions (i) and (ii), we obtain the following expression.

[0201] (γ S d ·γ L d )1 / 2 +(γ S p ·γ L p ) 1 / 2 +(γ S h ·γ L h ) 1 / 2 =γ L (1+cosθ) / 2···Mathematical expression (iii).

[0202] In fact, in the four solutions of water, ethylene glycol, formamide, and diiodomethane, the contact angle (θ) and the known components of the surface tension of the solution (γ) are considered. L d γ L p γ L h Substituting these values ​​into mathematical expression (iii), we solve the four simultaneous equations. The results allow us to calculate the surface energy (γ) and dispersion force component (γ0) of the solid. S d ), polar force component (γ) S p ), and hydrogen bonding components (γ) S h ).

[0203] (5) Analysis method of the composition of resin layer X surface

[0204] The composition of the resin layer X surface of the laminated film was analyzed using GCIB-TOF-SIMS (GCIB: Gas Cluster Ion Beam, TOF-SIMS: Time-of-Flight Secondary Ion Mass Spectrometry). The measurement conditions are described below. In the obtained graph, the peak intensity of the fragment detected with the highest intensity is set as K, and the fragment derived from polydimethylsiloxane (SiCH3) is considered... + The peak intensity of the fragment ion (M / Z = 43) was set as P, and its ratio P / K was calculated. When P / K < 0.1, it was determined that resin layer X substantially does not contain organosilicon compounds.

[0205] <Splashing Conditions>

[0206] Ion source: Argon cluster ion beam

[0207] <Testing Conditions>

[0208] Primary ion: Bi 3++ (25keV)

[0209] Secondary ion polarity: Negative

[0210] Mass range: m / z 0~1,000

[0211] Measurement range: 200×200μm 2 .

[0212] (6) The exothermic peak temperature (Tc) during the cooling process of a differential scanning calorimeter (DSC)

[0213] 1 g of release agent (A) or resin layer X cut from the surface of the laminated film was added to an aluminum cup with a diameter of 5 cm and dried in a hot air furnace at 80°C for 24 hours to prepare a dried solid sample of release agent (A) or resin layer X. 3 mg of the prepared solid sample was measured using a differential scanning calorimeter (DSC6220 manufactured by Hitachi High Tech Systems Co., Ltd.). First, under a nitrogen atmosphere, the temperature was increased from 25°C to 200°C at a rate of 20°C / min and held at 200°C for 5 minutes. Then, the temperature was decreased to -50°C at a rate of 20°C / min, and the peak temperature of the curve obtained during this cooling was measured. The average value of three measurements was set as (Tc). At this time, although sometimes more than two melting peak temperatures are observed in the above temperature range, and sometimes they become peak temperatures that can be observed in a multi-segment DSC chart called a shoulder (observed in the case of a chart where more than two peaks overlap), in this invention, the peak temperature with the largest absolute value of heat (unit: mW) on the vertical axis of the DSC chart is set as (Tc).

[0214] (7) X-ray absorption near-edge structure (XANES) spectrum

[0215] The side of the laminated film opposite to the X-plane of the resin layer was ground to adjust the thickness of the laminated film to 10 μm. A sample measuring 12 mm in length and 6 mm in width was cut from the ground laminated film and designated as the measurement sample. Next, the X-plane of the resin layer of the measurement sample was irradiated with X-rays, and the absorbance was measured to determine the X-ray absorption fine structure (XAFS) spectrum. The measurement and resolution conditions are described below.

[0216] Experimental facilities: Ritsumeikan University SR Center

[0217] Experimental station: BL11

[0218] Beam splitter: Diffraction grating beam splitter

[0219] Absorption edge: K (284.2 eV) absorption edge of carbon

[0220] E0: 287.319eV

[0221] Pre-edge range: -20 to 10 eV

[0222] Normalization range: 15–70 eV

[0223] Detection method: Partial electronic yield method using multi-channel plate measurement

[0224] Horizontal axis correction: The π-axis of highly oriented pyrolytic graphite ＊ Peak correction is 255.5 eV.

[0225] In the aforementioned XAFS spectrum, for the X-ray absorption near-edge structure (XANES) spectrum of the K absorption edge of carbon, the angle between the incident X-ray and the length direction vector of the resin layer of the laminated film is denoted as θ, and the spectral intensity of 293.5 eV obtained by the partial electron yield method is denoted as I(θ). The value obtained by subtracting the spectral intensity I(90°) when θ is 90° from the spectral intensity I(15°) when θ is 15° is denoted as I(15°)-I(90°).

[0226] (8) Peeling force of surface layer

[0227] The laminated film was cut into pieces 20 mm wide and 70 mm long. A ceramic slurry, prepared by mixing the following components, was applied to the resin layer X of the laminated film of the present invention using a coater, with the length direction as the travel direction, to a final thickness of 2 μm. The slurry was then dried in a hot air oven at 100°C for 1 minute to form a ceramic sheet (surface layer). Using a peeling device "VPA-2" manufactured by Kyowa Interface Science Co., Ltd. and a 1N force sensor, the opposite side of the surface layer was fixed to a measuring stage, and a 90° peeling test was conducted with the length direction as the travel direction and a peeling speed of 300 mm / min.

[0228] The average peel force from 15 to 35 mm was calculated from the peel force (N) versus displacement (mm) graph obtained by measurement. Five measurements were performed, and the average of the three measurements after removing the maximum and minimum values ​​was taken as the peel force of the laminated film. The following evaluation was conducted: A and above were designated as good, and B was designated as a level where there are no practical problems.

[0229] S: less than 20mN / cm

[0230] A: Above 20mN / cm and below 40mN / cm

[0231] B: Above 40mN / cm and below 80mN / cm

[0232] C: Above 80mN / cm

[0233] <Preparation of Ceramic Slurry>

[0234] ·BaTiO3 (manufactured by Sakai Chemical Industry Co., Ltd.) 85 parts by weight

[0235] • Polyvinyl butyral (manufactured by Sekisui Chemicals Co., Ltd., "Eslac" (registered trademark) BM-2) 15 parts by weight

[0236] · Dioctyl phthalate (manufactured by Kanto Chemical Co., Ltd.) 5 parts by weight

[0237] 150 parts by weight of toluene

[0238] • 150 parts by weight of ethanol (manufactured by Tokyo Chemical Co., Ltd.)

[0239] Zirconia balls with a diameter of 1 mm (YTZ-1 manufactured by Nikkato Co., Ltd.) were added at a weight of 2.5 times that of the slurry solution, and stirred at 55 rpm for 72 hours using an AS ONE MIX ROTOR VNRC-5.

[0240] (9) Electrostatic properties during surface layer peeling

[0241] The release film with ceramic sheets (surface layer) obtained in (8) above, which has ceramic sheets laminated on the surface layer side of the laminated film, was cut into 20 mm wide and 80 mm long. Then, the surface layer was peeled off from the resin layer of the release film by peeling test (300 mm / min) in (8). The voltage on the peeled ceramic sheet side was measured at 20°C in a 50% RH atmosphere using a digital electrostatic potential meter (Kasuga Electric Co., Ltd., KSD-0103). The absolute value of the voltage was evaluated by the following four criteria: S is set as very good, A is set as good, and B is set as a level that is practically problem-free.

[0242] S: ≤0.05kV

[0243] A: Above 0.05kV and below 0.20kV

[0244] B: Above 0.20kV and below 0.50kV

[0245] C: >0.50kV

[0246] (10) Evaluation of antistatic agent shedding

[0247] The laminated film was cut into 110mm, 110mm sizes. The ceramic slurry prepared in (8) was coated onto the resin layer X of the laminated film of the present invention with a final thickness of 5μm using a coater. The film was then dried in a hot air oven at 100°C for 1 minute to form a ceramic sheet (surface layer). The surface resistivity (SR1) of the surface layer was measured using the method in (3).

[0248] The release liner of one side of the 3M acrylic adhesive sheet (“OCA” (registered trademark) 8146-2) is peeled off and bonded to the surface layer of the ceramic laminate. Then, the acrylic adhesive sheet is peeled off from the laminate, so that the surface layer is transferred to the acrylic adhesive sheet side. Regarding the transferred surface layer, the surface resistivity value (SR2) is measured using the method in (3), and the peeling performance of the antistatic agent is evaluated by (SR1) / (SR2). A is set as good, and B is set as a level that has no practical problems.

[0249] A: (SR1) / (SR2) is less than 10 (no transfer)

[0250] B: (SR1) / (SR2) is 10 or higher and less than 100

[0251] C: (SR1) / (SR2) is 100 or higher

[0252] <Resins, etc. used in the manufacture of laminated films>

[0253] <Mold Release Agent (A)>

[0254] • Release agent (A-1): Long-chain alkyl resin 1

[0255] 200 parts by mass of xylene and 600 parts by mass of octadecyl isocyanate were added to a four-necked flask and heated with stirring. Starting from the moment the xylene began to reflux, 100 parts by mass of polyvinyl alcohol (PVA) with an average degree of polymerization of 500 and a degree of saponification of 88 mol% was added in small amounts at 10-minute intervals over approximately 2 hours. After the addition of PVA was complete, the reaction was further refluxed for another 2 hours to finish the reaction. The reaction mixture was cooled to approximately 80°C and then added to methanol, causing the reaction product to precipitate as a white precipitate. After filtering and separating the precipitate, 140 parts by mass of xylene were added and heated to completely dissolve it. Then, methanol was added again to precipitate the precipitate. This process was repeated several times. The precipitate was then washed with methanol and dried and pulverized to obtain a resin containing long-chain alkyl groups (A-1): with polymethylene as the main chain and alkyl groups having 18 carbon atoms in the side chains. This was diluted with water to a concentration of 20 parts by mass.

[0256] • Release agent (A-2): Long-chain alkyl resin 2

[0257] In a 25 mL pressure-resistant glass ampoule for polymerization, methyl methacrylate (MMA) (manufactured by Kanto Chemical Co., Ltd.), α,α'-azobisisobutyronitrile (AIBN) (manufactured by Kanto Chemical Co., Ltd.) as a polymerization initiator, cumyl dithiobenzoate (CDB) as a RAFT agent, and toluene as a solvent were added in a weight (g) ratio of MMA / CDB / AIBN = 2.92 / 0.03 / 0.007 / 2.27. Next, the mixed solution in the ampoule was degassed twice by a freeze-drying method, and then the ampoule was sealed and heated in an oil bath at 100°C for 18 hours to obtain polymerization solution 1. Next, in the reaction solution inside the ampoule, docosyl acrylate, AIBN as a polymerization initiator, and toluene as a solvent were added at a weight ratio of 1.37 / 0.003 / 1.3 g. After two freeze-degassing cycles, the ampoule was sealed and heated at 100°C for 48 hours. Then, 1 drop of the polymerization solution was added to 20 times its weight of hexane, and the mixture was stirred to precipitate a solid. The resulting solid was filtered and vacuum-dried overnight at 40°C to obtain a long-chain alkyl resin (A-2) with 22 carbon atoms. The obtained long-chain alkyl resin (A-2) was emulsified as follows to prepare an aqueous resin emulsion. 375g of water was added to a 1L homogenizer, followed by 45g of polyoxyethylene nonylphenyl ether, 30g of polyoxyethylene polyoxypropylene glycol, 200g of long-chain alkyl resin (A-2), and 150g of toluene. The mixture was then heated to 70°C and stirred uniformly. After emulsification in a pressure homogenizer, the toluene was further removed by distillation under reduced pressure and heating.

[0258] • Release agent (A-3): Long-chain alkyl resin 3

[0259] Instead of octadecyl isocyanate, dodecyl isocyanate was used. Otherwise, a resin containing long-chain alkyl groups (A-3: alkyl group with polymethylene as the main chain and 12 carbon atoms in the side chain) was synthesized by the same method as the resin containing long-chain alkyl groups (A-1).

[0260] • Release agent (A-4): Long-chain alkyl resin 4

[0261] An aqueous coating solution (A-4) was prepared by dissolving an acrylic resin containing long-chain alkyl groups formed from the following copolymer composition in water containing 5 wt% isopropanol and 5 wt% n-butyl solvent. It should be noted that the long-chain alkyl group of lauryl methacrylate has 12 carbon atoms.

[0262] <Copolymer Components>

[0263] 70% by weight of lauryl methacrylate

[0264] 25% by weight of methacrylic acid

[0265] 5% by weight of 2-hydroxyethyl methacrylate.

[0266] • Release agent (A-5): Silicone-based release agent

[0267] 100 parts by mass of thermosetting silicone resin [manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KS-847H"] and 1 part by mass of catalyst [manufactured by Shin-Etsu Chemical Co., Ltd., trade name "CAT-PL-50T"] were diluted with toluene to obtain a solution with a solid content of 1.5 parts by mass.

[0268] <Adhesive Resin (B)>

[0269] • Adhesive resin (B-1): Acrylic resin (containing hydroxyl groups)

[0270] In a stainless steel reaction vessel, methyl methacrylate (α), ethyl acrylate (β), 2-hydroxyethyl acrylate (γ), and acrylonitrile (δ) were added in a mass ratio of (α) / (β) / (γ) / (δ) = 60 / 32 / 6 / 2. Sodium dodecylbenzenesulfonate, acting as an emulsifier, was added in a 2-part ratio relative to a total of 100 parts by mass of (α) to (δ), and the mixture was stirred to prepare mixture 1. Next, a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was prepared. 60 parts by mass of the above mixture 1, 200 parts by mass of isopropanol, and 5 parts by mass of potassium persulfate as a polymerization initiator were added to the reaction apparatus, and the mixture was heated to 60°C to prepare mixture 2. Mixture 2 was maintained at 60°C for 20 minutes. Next, mixture 3, consisting of 40 parts by mass of mixture 1, 50 parts by mass of isopropanol, and 5 parts by mass of potassium persulfate, was prepared. Next, mixture 3 was added dropwise to mixture 2 over 2 hours using a dropping funnel to prepare mixture 4. Mixture 4 was then heated to 60°C and maintained for 2 hours. After cooling mixture 4 to below 50°C, it was transferred to a container equipped with a stirrer and a vacuum distillation unit. 60 parts by weight of 25% ammonia and 900 parts by weight of pure water were added, and isopropanol and unreacted monomers were recovered under reduced pressure while heating to 60°C, yielding an acrylic resin (B-1) dispersed in pure water.

[0271] • Adhesive resin (B-2): Acrylic resin (containing hydroxyl and carboxyl groups)

[0272] For the starting materials added to the stainless steel reaction vessel, methyl methacrylate (α), ethyl acrylate (β), 2-hydroxyethyl acrylate (γ), acrylonitrile (δ) / acrylic acid (ε) were added in a mass ratio of (α) / (β) / (γ) / (δ) / (ε) = 55 / 32 / 6 / 2 / 5, making a total of 100 parts by mass. Otherwise, the same procedure as for the binder resin (B-1) was followed to obtain the acrylic resin (B-2).

[0273] • Adhesive resin (B-3): Polyester resin

[0274] A thermosetting polyester resin aqueous dispersion (manufactured by Koyo Chemical Industry Co., Ltd., Z-836, solids concentration 15% by weight) was used.

[0275] <Crosslinking agent (C)>

[0276] • Crosslinking agent (C-1): Melamine resin (hydroxymethylated melamine)

[0277] It uses "Nikkalac" (registered trademark) MW-035 (70% solid content by mass, solvent: water) manufactured by Sanwa Kemikal Co., Ltd.

[0278] • Crosslinking agent (C-2): Carbodiimide compound

[0279] It uses "Carboji Light" (registered trademark) V-04 (solid content concentration 40% by mass, solvent: water) manufactured by Nisshin Textile Co., Ltd.

[0280] <Antistatic Agent (D)>

[0281] • Antistatic agent (D-1): CNT aqueous dispersion 1

[0282] 1.0 mg of a linear two-layer CNT (manufactured by Sien Slaboratories, 5 nm in diameter, aspect ratio 3000), 3.0 mg of sodium carboxymethyl cellulose (CMC-Na) as a CNT dispersant, and 666 mg of water were added to a sample tube to prepare a CNT aqueous dispersion. The dispersion was then subjected to ultrasonic irradiation for 30 minutes using an ultrasonic disruptor (Tokyo Rikaki K. Co., Ltd. VCX-502, 250 W output, direct irradiation) to obtain a uniform CNT aqueous dispersion (D-1) consisting of CNTs and CNT dispersant (CNT concentration 0.15 wt%, CNT dispersant 0.45 wt%, CNT dispersant / CNT = 3.0).

[0283] • Antistatic agent (D-2): Polythiophene compound

[0284] In 1887 parts by mass of an aqueous solution containing 20.8 parts by mass of polystyrene sulfonic acid as an acidic polymer compound, 49 parts by mass of a 1% by mass aqueous solution of iron(III) sulfate, 8.8 parts by mass of 3,4-ethylenedioxythiophene as a thiophene compound, and 117 parts by mass of a 10.9% by mass aqueous solution of persulfuric acid were added. The mixture was stirred at 18 °C for 23 hours. Then, 154 parts by mass of a cation exchange resin (“Lewatit” (registered trademark) Monoplus S100H; manufactured by Lanxess) and 232 parts by mass of an anion exchange resin (“Lewatit” (registered trademark) Monoplus M800; manufactured by Lanxess) were added to the mixture. After stirring for 2 hours, the ion exchange resins were separated by filtration, and an antistatic agent (D-2) composed of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (solid component concentration: 1.3% by weight) was obtained.

[0285] · Antistatic agent (D-3): CNT aqueous dispersion 2

[0286] CNT aqueous dispersion 2 was prepared as described below.

[0287] First, 1.0 mg of CNT (2-layer CNT: manufactured by Science Laboratories Co., Ltd., average diameter 5 nm), 1.0 mg of CMC-Na as a CNT dispersant, and 248 mg of water were added to a 50 mL sample tube to prepare a CNT aqueous dispersion. Ultrasonic irradiation was performed for 30 minutes using an ultrasonic crusher (VCX-502 manufactured by Tokyo Rika Kikai Co., Ltd., output 250 W, direct irradiation) to obtain a uniform CNT aqueous dispersion (CNT concentration 0.40 wt%, CNT dispersant 0.40 wt%, (B) / (A) = 0.5).

[0288] · Antistatic agent (D-4): Carbon nanofibers

[0289] Carbon nanofibers with an average diameter of 15 nm and an average length of 1 μm [(manufactured by Gemco Co., Ltd., product name “CNF-T”, tubular, 3% by mass cyclohexanone dispersion type] were used.

[0290] <Crosslinking catalyst>

[0291] · Catalyst 1: Dodecylbenzenesulfonic acid

[0292] Namboku Kasei Co., Ltd., “NACURE” (registered trademark) 5528 (manufacturer: KING INDUSTRIES, NACURE DDBSA series: dodecylbenzenesulfonic acid catalyst (blocked acid catalyst)) was used.

[0293] · Catalyst 2: Platinum catalyst

[0294] A platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "CAT-PL-50T") was used.

[0295] (Example 1)

[0296] • Resin composition for resin layer formation:

[0297] The mold release agent (A-1), adhesive resin (B-1), and crosslinking agent (C-1) were mixed in a solids mass ratio of (A-1) / (B-1) / (C-1) = 25 / 30 / 45. Next, antistatic agent (D-1) was added in a solids mass ratio of 10 parts to 100 parts by mass of the total mixture of mold release agent (A-1), adhesive resin (B-1), and crosslinking agent (C-1), along with 5 parts by mass of catalyst 1. The solids concentration was adjusted by adding water according to the coating method and target thickness described later. Furthermore, to improve the coatability to the polyester film, an acetylene glycol-based surfactant (Nikshin Chemical Industry Co., Ltd. "Orfin" (registered trademark) EXP.4200) was added in a solids mass ratio of 0.1 parts to 100 parts by mass of the mixed resin composition.

[0298] • Polyester film:

[0299] PET granules (intrinsic viscosity 0.64 dl / g) containing two types of particles (4 parts by mass of silica particles with a primary particle size of 0.3 μm and 2 parts by mass of calcium carbonate particles with a primary particle size of 0.8 μm) were thoroughly vacuum dried and then fed into an extruder to melt at 280°C. The granules were extruded in sheet form from a T-die and then electrostatically cast onto a mirror casting drum with a surface temperature of 25°C for cooling and solidification, thus obtaining an unstretched film (film A). This unstretched film was then heated to 90°C and stretched 3.1 times along its length to produce a uniaxially stretched film (film B).

[0300] • Laminated membrane

[0301] After subjecting the uniaxially stretched film to corona discharge treatment in air, the resin composition prepared by the method described in the section on resin composition for resin layer formation was coated using a wire bar coater to a coating thickness of approximately 6 μm. Next, the two ends of the uniaxially stretched film coated with the resin composition were held in the width direction by clamps and guided to a tenter frame, where the solvent of the resin composition was dried in a preheating zone at an atmosphere temperature of 90–100°C. Then, it was continuously stretched 3.6 times in the width direction in a stretching zone at 100°C, followed by a heat treatment at 230°C for 20 seconds to form resin layer X. Finally, a 5% relaxation treatment was performed in the width direction at the same temperature to obtain a laminated film with completed polyester film crystal orientation. The characteristics of the obtained laminated film are shown in Tables 3 and 4.

[0302] (Examples 2-7, Comparative Examples 1-3)

[0303] The composition of the resin composition was changed as described in Table 1, except that a laminated film was obtained by the same method as in Example 1. The properties of the resulting laminated film are shown in Tables 3 and 4.

[0304] (Example 8)

[0305] Using the resin composition of Example 1, a laminated film was obtained by the following method. As the substrate, a PET film "Lumira" (registered trademark) T60 (substrate thickness 50 μm) manufactured by Tore Co., Ltd. was used. The resin composition was applied to the substrate using a wire rod. Next, to prevent deformation caused by heat, an SUS sheet film of the same type as the film was prepared, held without gaps on all four sides using double-clamps, and then dried / cured in a hot air oven at 230°C for 2 minutes to obtain the laminated film. The properties of the obtained laminated film are shown in Tables 3 and 4.

[0306] (Comparative Example 4)

[0307] The laminated film is fabricated as described below.

[0308] First, adhesive resin (B-3) was added to the antistatic agent (D-3), and the mixture was stirred at 500 rpm for 15 minutes using an electromagnetic stirrer to obtain a CNT dispersion. The weight ratio of the antistatic agent (D-3), CNT dispersant, and adhesive resin (B-3) in the CNT dispersion (with the total weight of (D-3), CNT dispersant, and (B-3) set at 100% by weight) is as follows.

[0309] (D-3) 4.0% by weight

[0310] CNT dispersant 2.0% by weight

[0311] (B-3) 94.0% by weight

[0312] At this point, the weight ratio of CNT dispersant to (D-3) is 0.5.

[0313] Next, an acrylic resin (A-4) containing long-chain alkyl groups prepared from the following copolymer composition is mixed with the above-mentioned CNT dispersion in such a way that [the total weight of (D-3) and CNT dispersant and (B-3)] / [the weight of (A-4)] = 100 parts by weight / 10 parts by weight to prepare a coating resin composition.

[0314] Next, after thoroughly vacuum-drying the essentially particle-free PET granules (intrinsic viscosity 0.63 dl / g), they were fed into an extruder and melted at 285°C. The granules were extruded in sheet form from a T-die and then electrostatically cast onto a mirror-finished casting drum at a surface temperature of 25°C for cooling and solidification. This unstretched film was then heated to 90°C and stretched 3.4 times along its length to produce a uniaxially stretched film (B film). The film was then subjected to corona discharge treatment in air.

[0315] Next, the coating resin composition was coated onto the corona discharge treated surface of the uniaxially stretched film using a bar coater. The uniaxially stretched film coated with the coating resin composition was held at both ends in the width direction by clamps and guided to a preheating zone. After setting the atmosphere temperature to 75°C, a radiant heater was used to set the atmosphere temperature to 110°C, followed by a setting to 90°C to dry the coating resin composition. Then, it was continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120°C, followed by a 20-second heat treatment in a heat treatment zone (heat setting zone) at 230°C, resulting in a laminated film with completed crystal orientation.

[0316] (Comparative Example 5)

[0317] The laminated film was prepared as follows. 100 parts by weight of silicone release agent (A-5) and 1 part by weight of catalyst 2 (platinum catalyst) were diluted with toluene to obtain a solution with a solid content concentration of 1.5% by weight. Antistatic agent (D-4) was added to this solution at a content of 5% by weight of the total solid content (antistatic release agent layer) to prepare a coating solution. Next, this coating solution was uniformly coated onto a 38 μm thick polyethylene terephthalate (PET) film [manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., trade name "T-100"] using a Mayer rod to a thickness of 0.1 μm after drying. Then, the film was heated in a dryer at 130°C for 1 minute to form a resin layer, thus producing the laminated film.

[0318] (Examples 9, 10, and Comparative Example 6)

[0319] The resin compositions described in Tables 1 and 2 were applied to each surface using a wire-bar coater to a coating thickness of approximately 6 μm. Specifically, the side of the uniaxially stretched film substrate opposite to resin layer X was also subjected to corona discharge treatment in air. The resin composition for forming resin layer Y described in Table 2 was applied to each surface using a wire-bar coater to a coating thickness of approximately 6 μm. Resin layer Y was formed simultaneously with resin layer X by the same drying / stretching / heat treatment as resin layer X. Otherwise, a laminated film was obtained using the same method as in Example 1. The characteristics of the obtained laminated film are shown in Tables 3 and 4.

[0320] (Examples 11 and 12)

[0321] As raw materials for the polyester film, PET pellets containing recycled raw materials in the proportions shown in Table 1 (Example 11) and biomass raw materials (Example 12) were used. Otherwise, a laminated film was obtained using the same method as in Example 3. The characteristics of the obtained laminated film are shown in Tables 2 and 3. It should be noted that the recycled raw materials referred to here are materials from which the uncoated portions removed during the film-making process of the polyester films in Examples 1-10 were finely chopped and used in the polyester film-making process, mixed with the original raw materials. On the other hand, the biomass raw material was PET with a biomass content of 15%, and a portion of the ethylene glycol unit was derived from plant-based PET.

[0322] (Example 13)

[0323] As the raw material for the polyester film, PET particles containing the proportions of recycled raw materials shown in Table 1, as in Example 11, were used. Otherwise, the laminated film was obtained by the same method as in Example 10.

[0324] [Table 1]

[0325]

[0326] [Table 2]

[0327]

[0328] [Table 3]

[0329]

[0330] [Table 4]

[0331] Table 4

[0332]

[0333] Industry availability

[0334] The multilayer film of the present invention combines the light peelability and antistatic properties of the resin layer, thereby exhibiting excellent processability in the process of peeling off the surface layer. Furthermore, it avoids contamination caused by organosilicon and the shedding of antistatic agents. Therefore, it is suitable for use as a process film in the manufacturing process of electronic components such as multilayer ceramic capacitors and inductors, as well as in the manufacturing process of batteries such as lithium-ion batteries and all-solid-state batteries.

Claims

1. A laminated film having a resin layer X comprising an antistatic agent on at least one surface of a thermoplastic resin substrate film, wherein the laminated film satisfies all of the following conditions (1) to (3). (1) The average nitrogen to carbon content ratio per 1 nm of the resin layer X, calculated using the nitrogen to carbon ratio (N / C) and the thickness of the resin layer X, is 0.0030 nm. -1 The nitrogen to carbon ratio mentioned above was calculated using the high-resolution Rutherford backscattering method (HR-RBS), and the thickness is measured in nm. (2) The surface resistivity of the resin layer X is 1.0 × 10⁻⁶. 10 Below Ω / □ (3) The surface free energy of the resin layer X is greater than 20.0 mN / m and less than 30.0 mN / m. The resin layer X contains a long-chain alkyl resin as a release agent, a melamine compound as a crosslinking agent, and an acrylic resin as an adhesive resin. The antistatic agent contained in the resin layer X is a conductive carbon material. When the total amount of release agent, adhesive resin, and crosslinking agent is set to 100 parts by weight, the content of release agent is 10 parts by weight or more and 50 parts by weight or less, the content of crosslinking agent is 40 parts by weight or more, and the content of antistatic agent is 0.05 parts by weight or more and 20.0 parts by weight or less.

2. The laminated film according to claim 1, wherein the antistatic agent contained in the resin layer X is carbon nanotubes.

3. The laminated membrane according to claim 1 or 2, wherein when the surface of the resin layer X is analyzed by time-of-flight secondary ion mass spectrometry, the ratio of the peak intensity P of the fragment derived from polydimethylsiloxane to the peak intensity K of the fragment detected at maximum intensity, i.e., P / K[-], is less than 0.

01.

4. The laminated film according to claim 1 or 2, wherein the resin layer X comprises a long-chain alkyl resin as a release agent, and the exothermic peak temperature Tc during the cooling process of heating the long-chain alkyl resin from 25°C to 200°C at 20°C / min using a differential scanning calorimeter (DSC) and then cooling it from 200°C to -50°C at 20°C / min is above 30°C and below 90°C.

5. The laminated film according to claim 1 or 2, regarding the X-ray absorption fine structure (XAFS) spectrum of carbon K absorption edge in the X-ray absorption fine structure (XANES) spectrum of the resin layer X measured by partial electron yield method, when the angle between the incident X-ray and the resin layer is set as θ, and the spectral intensity of 293.5 eV is set as I(θ), I(15°) - I(90°) ≥ 0.10 is satisfied.

6. The laminated film according to claim 1, wherein the long-chain alkyl resin is a block copolymer.

7. The laminated membrane according to claim 1 or 2, wherein the thermoplastic resin substrate membrane is a polyester membrane comprising at least one of biomass raw materials and recycled raw materials.

8. The laminated film according to claim 1 or 2, wherein it has a resin layer Y on a side opposite to the resin layer X, and the surface resistivity of either side is 1.0 × 10⁻⁶. 10 Below Ω / □.

9. The laminated film according to claim 8, wherein the resin layer Y comprises carbon nanotubes.

10. The laminated film according to claim 1 or 2, which is used in the manufacturing process of electronic components or battery components.

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